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FIELD OF THE INVENTION
The present invention relates to information delivery, and relates more specifically to a cache for information objects that are to be delivered efficiently and at high speed over a network to a client.
BACKGROUND OF THE INVENTION
Several important computer technologies rely, to a great extent, upon rapid delivery of information from a central storage location to remote devices. For example, in the client/server model of computing, one or more servers are used to store information. Client computers or processes are separated from the servers and are connected to the servers using a network. The clients request information from one of the servers by providing a network address of the information. The server locates the information based on the provided network address and transmits it over the network to the client, completing the transaction.
The World Wide Web is a popular application of the client/server computing model. FIG. 1 is a simplified block diagram of the relationship between elements used in a Web system. One or more web clients 10a, 10b, each of which is a computer or a software process such as a browser program, are connected to a global information network 20 called the Internet, either directly or through an intermediary such as an Internet Service Provider, or an online information service.
A web server 40 is likewise connected to the Internet 20 by a network link 42. The web server 40 has one or more internet network addresses and textual host names, associated in an agreed-upon format that is indexed at a central Domain Name Server (DNS). The server contains multimedia information resources, such as documents and images, to be provided to clients upon demand. The server 40 may additionally or alternatively contain software for dynamically generating such resources in response to requests.
The clients 10a, 10b and server 40 communicate using one or more agreed-upon protocols that specify the format of the information that is communicated. A client 10a looks up network address of a particular server using DNS and establishes a connection to the server using a communication protocol called the Hypertext Transfer Protocol (HTTP). A Uniform Resource Locator (URL) uniquely identifies each information object stored on or dynamically generated by the server 40. A URL is a form of network address that identifies the location of information stored in a network.
A key factor that limits the performance of the World Wide Web is the speed with which the server 40 can supply information to a client via the Internet 20. Performance is limited by the speed, reliability, and congestion level of the network route through the Internet, by geographical distance delays, and by server load level. Accordingly, client transaction time can be reduced by storing replicas of popular information objects in repositories geographically dispersed from the server. Each local repository for object replicas is generally referred to as a cache. A client may be able to access replicas from a topologically proximate cache faster than possible from the original web server, while at the same time reducing Internet server traffic.
In one arrangement, as shown in FIG. 1, the cache is located in a proxy server 30 that is logically interposed between the clients 10a, 10b and the server 40. The proxy server provides a "middleman" gateway service, acting as a server to the client, and a client to the server. A proxy server equipped with a cache is called a caching proxy server, or commonly, a "proxy cache".
The proxy cache 30 intercepts requests for resources that are directed from the clients 10a, 10b to the server 40. When the cache in the proxy 30 has a replica of the requested resource that meets certain freshness constraints, the proxy responds to the clients 10a, 10b and serves the resource directly. In this arrangement, the number and volume of data transfers along the link 42 are greatly reduced. As a result, network resources or objects are provided more rapidly to the clients 10a, 10b.
A key problem in such caching is the efficient storage, location, and retrieval of objects in the cache. This document concerns technology related to the storage, location, and retrieval of multimedia objects within a cache. The object storage facility within a cache is called a "cache object store" or "object store".
To effectively handle heavy traffic environments, such as the World Wide Web, a cache object store needs to be able to handle tens or hundreds of millions of different objects, while storing, deleting, and fetching the objects simultaneously. Accordingly, cache performance must not degrade significantly with object count. Performance is the driving goal of cache object stores.
Finding an object in the cache is the most common operation and therefore the cache must be extremely fast in carrying out searches. The key factor that limits cache performance is lookup time. It is desirable to have a cache that can determine whether an object is in the cache (a "hit") or not (a "miss") as fast as possible. In past approaches, caches capable of storing millions of objects have been stored in traditional file system storage structures. Traditional file systems are poorly suited for multimedia object caches because they are tuned for particular object sizes and require multiple disk head movements to examine file system metadata. Object stores can obtain higher lookup performance by dedicating DRAM memory to the task of object lookup, but because there are tens or hundreds of millions of objects, the memory lookup tables must be very compact.
Once an object is located, it must be transferred to the client efficiently. Modem disk drives offer high performance when reading and writing sequential data, but suffer significant performance delays when incurring disk head movements to other parts of the disk. These disk head movements are called "seeks". Disk performance is typically constrained by the drive's rated seeks per second. To optimize performance of a cache, it is desirable to minimize disk seeks, by reading and writing contiguous blocks of data.
Eventually, the object store will become full, and particular objects must be expunged to make room for new content. This process is called "garbage collection". Garbage collection must be efficient enough that it can run continually without providing a significant decrease in system performance, while removing objects that have the least impact on future cache performance.
Past Approaches
In the past, four approaches have been used to structure cache object stores: using the native file system, using a memory-blocked "page" cache, using a database, and using a "cyclone" circular storage structure. Each of these prior approaches has significant disadvantages.
The native file system approach uses the file system of an operating system running on the server to create and manage a cache. File systems are designed for a particular application in mind: storing and retrieving user and system data files. File systems are designed and optimized for file management applications. They are optimized for typical data file sizes and for a relatively small number of files (both total and within one folder/directory). Traditional file systems are not optimized to minimize the number of seeks to open, read/write, and close files. Many file systems incur significant performance penalties to locate and open files when there are large numbers of files present. Typical file systems suffer fragmentation, with small disk blocks scattered around the drive surface, increasing the number of disk seeks required to access data, and wasting storage space. Also, file systems, being designed for user data file management, include facilities irrelevant to cache object stores, and indeed counter-productive to this application. Examples include: support for random access and selective modification, file permissions, support for moving files, support for renaming files, and support for appending to files over time. File systems are also invest significant energy to minimize any data loss, at the expense of performance, both at write time, and to reconstruct the file system after failure. The result is that file systems are relatively poorly for handling the millions of files that can be present in a cache of Web objects. File systems don't efficiently support the large variation in Internet multimedia object size--in particular they typically do not support very small objects or very large objects efficiently. File systems require a large number of disk seeks for metadata traversal and block chaining, poorly support garbage collection, and take time to ensure data integrity and to repair file systems on restart.
The page cache extends file systems with a set of fixed sized memory buffers. Data is staged in and out of these buffers before transmission across the network. This approach wastes significant memory for large objects being sent across slow connections.
The database system approach uses a database system as a cache. Generally, databases are structured to achieve goals that make them inappropriate for use as an object cache. For example, they are structured to optimize transaction processing. To preserve the integrity of each transaction, they use extensive locking. As a result, as a design goal they favor data integrity over performance factors such as speed. In contrast, it is acceptable for an object cache to lose data occasionally, provided that the cache does not corrupt objects, because the data always can be retrieved from the server that is original source of the data. Databases are often optimized for fast write performance, since write speed limits transaction processing speed. However, in an object cache, read speed is equally important. Further, databases are not naturally good at storing a vast variety of object sizes while supporting streaming, pipelined I/O in a virtual memory efficient manner. Databases commonly optimized for fixed record size sizes. Where databases support variable record sizes, they contain support for maintaining object relationships that are redundant, and typically employ slow, virtual memory paging techniques to support streaming, pipelined I/O.
In a cyclonic file system, data is allocated around a circular storage structure. When space becomes full, the oldest data is simply removed. This approach allows for fast allocation of data, but makes it difficult to support large objects without first staging them in memory, suffers problems with fragmentation of data, and typically entails naive garbage collection that throws out the oldest object, regardless of its popularity. For a modest, active cache with a diverse working set, such first-in-first-out garbage collection can throw objects out before they get to be reused.
The fundamental problem with the above approaches for the design of cache object stores is that the solution isn't optimized for the constraints of the problem. These approaches all represent reapplication of existing technologies to a new application. None of the applications above are ideally suited for the unique constraints of multimedia, streaming, object caches. Not only do the above solutions inherently encumber object caches with inefficiencies due to their imperfect reapplication, but they also are unable to effectively support the more unique requirements of multimedia object caches. These unique requirements include the ability to disambiguate and share redundant content that is identical, but has different names, and the opposite ability to store multiple variants of content with the same name, targeted for particular clients, languages, data types, etc.
Based on the foregoing, there is a clear need to provide an object cache that overcomes the disadvantages of these prior approaches, and is more ideally suited for the unique requirements of multimedia object caches. In particular:
1. there is a need for an object store that can store hundreds of millions of objects of disparate sizes, and a terabyte of content size in a memory efficient manner;
2. there is a need for an object store that can determine if a document is a "hit" or a "miss" quickly, without time-consuming file directory lookups;
3. there is a need for a cache that minimizes the number of disk seeks to read and write objects;
4. there is a need for an object store that permits efficient streaming of data to and from the cache;
5. there is a need for an object store that supports multiple different versions of targeted alternates for the same name;
6. there is a need for an object store that efficiently stores large numbers of objects without content duplication;
7. there is a need for an object store that can be rapidly and efficiently garbage collected in real-time, insightfully selecting the documents to be replaced to improve user response speed, and traffic reduction;
8. there is a need for an object store that that can restart to full operational capacity within seconds after software or hardware failure without data corruption and with minimal data loss.
This document concerns technology directed to accomplishing the foregoing goals. In particular, this document describes methods and structures related to the time-efficient and space-efficient storage, retrieval, and maintenance of objects in a large object store. The technology described herein provides for a cache object store for a high-performance, high-load application having the following general characteristics:
1. High performance, measured in low latency and high throughput for object store operations, and large numbers of concurrent operations;
2. Large cache support, supporting terabyte caches and billions of objects, to handle the Internet's exponential content growth rate;
3. Memory storage space efficiency, so expensive semiconductor memory is used sparingly and effectively;
4. Disk storage space efficiency, so large numbers of Internet object replicas can be stored within the finite disk capacity of the object store;
5. Alias free, so that multiple objects or object variants, with different names, but with the same content identical object content, will have the object content cached only once, shared among the different names;
6. Support for multimedia heterogeneity, efficiently supporting diverse multimedia objects of a multitude of types with size ranging over six orders of magnitude from a few hundred bytes to hundreds of megabytes;
7. Fast, usage-aware garbage collection, so less useful objects can be efficiently removed from the object store to make room for new objects;
8. Data consistency, so programmatic errors and hardware failures do not lead to corrupted data;
9. Fast restartability, so an object cache can begin servicing requests within seconds of restart, without requiring a time-consuming database or file system check operation;
10. Streaming, so large objects can be efficiently pipelined from the object store to slow clients, without staging the entire object into memory;
11. Support for content negotiation, so proxy caches can efficiently and flexibly store variants of objects for the same URL, targeted on client browser, language, or other attribute of the client request; and
12. General-purpose applicability, so that the object store interface is sufficiently flexible to meet the needs of future media types and protocols.
SUMMARY OF THE INVENTION
The foregoing needs and other needs are addressed by the present invention, which provides, in one aspect, in a cache for information objects that comprises a directory table that indexes each of the information objects in one of a plurality of buckets, an open directory comprising a list of changes associated with each of the buckets, a set of volatile object aggregation buffers, and a set of disk-based object pools, a method for ensuring the integrity of cache storage in the presence of software failures, comprising the steps of ensuring the integrity of cache storage in the presence of software failures; whereby after a cache restart, all previously cached objects are consistent, in that pre-failure objects are either completely present or completely absent from the cache, and there is no truncation, corruption, or false aliasing of cache content.
A feature of this aspect is ensuring the integrity of the cache is carried out in a manner requiring no database reconstruction after restart, allowing immediate operation, by careful use of synchronization, and tolerance of a small loss of cached data. Another feature is storing objects that are written to the cache in a volatile write-aggregation buffer, and assigning a meta-data reference to such storage in the open directory.
Yet another feature is writing and synchronizing fill aggregation buffers to disk. Still another feature involves steps in which blocks of the open directory table are copied to directory tables and synchronized to disk if and only if the referenced object has itself been written and synchronized to disk. Another feature is periodically carrying out a garbage collection task in which undesirable fragments of objects are deleted from storage arenas, by deleting the metadata from the directory table and committing the deleted metadata to disk.
Another feature involves periodically carrying out a garbage collection task that evacuates desirable fragments of objects from arenas by deleting the metadata from the directory table; committing the deleted metadata to disk; and evacuating the fragment to an aggregation buffer. Still another feature relates to making the arena available for subsequent use by marking the arena free in a pool header, and writing and synchronizing the pool header to non-volatile storage.
According to another aspect, the invention comprises, in a cache for information objects comprising a directory table that indexes each of the information objects in one of a plurality of buckets, an open directory comprising a list of changes associated with each of the buckets, a set of volatile object aggregation buffers, and a set of disk-based object pools, a method of synchronizing the cache, comprising the steps of writing an information object to cache by creating meta-data in the open directory and by writing and syncing the object data to non-volatile storage; periodically, for each piece of meta-data in the open directory, determining whether the data the meta-data points to is already synchronized, and if so, copying the meta-data from the open directory table that points to the stable data to the directory table and sync the changes to disk; carrying out garbage collection on an arena by, for each fragment in the arena, deleting and writing to disk the directory meta-data pointing to the fragment; modifying the pool header so as to mark the arena empty; and writing and syncing the pool header to disk.
Another feature of the first aspect involves (F) obtaining a length of the fragment from a message of a client that requests the information object from the cache; (G) identifying a selected arena having free space sufficient greater than the length of the fragment; (H) obtaining a lock on the selected aggregation buffer; (I) allocating space for the fragment in the selected arena; (J) releasing the lock from the selected arena; and (K) storing the fragment in the selected arena.
In another aspect, the invention involves, in a cache for information objects comprising a directory table that indexes each of the information objects in one of a plurality of blocks that is stored in one of a plurality of buckets, and an open directory comprising a list of changes associated with each of the buckets, a method of managing the cache, comprising the steps of (A) receiving a key that identifies an information object requested by a client of the cache; (B) identifying a selected bucket from among the plurality of buckets that corresponds to the key and identifying a selected block from among the plurality of blocks that corresponds to the key; (C) when the block is not being created or destroyed, storing a reader count of processes that are reading the block, and providing a copy of the block to the client.
One feature of this aspect involves (D) when the block is not being created or destroyed, (D1) storing a writer count of processes that are writing the block; (D2) marking a copy of the block as being modified; and (D3) providing the copy of the block to the client. Another feature involves (E) when the block is not deleted and the writer count and the reader count are zero, (E1) initializing the block based on the key; (E2) incrementing the writer count and the reader count; (E3) providing the copy of the block to the client.
Yet another feature is (F) checking in the copy of the block to the cache by the steps of (F1) decrementing the writer count when the block is being modified, and decrementing the reader count otherwise; (F2) storing the copy of the block in the open directory; and (F3) marking the block as deleted when a delete checkin value is provided.
The invention also encompasses an apparatus, computer system, computer program product, and a computer data signal embodied in a carrier wave configured according to the foregoing aspects.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
FIG. 1 is a block diagram of a client/server relationship;
FIG. 2 is a block diagram of a traffic server;
FIG. 3A is a block diagram of transformation of an object into a key;
FIG. 3B is a block diagram of transformation of an object name into a key;
FIG. 4A is a block diagram of a cache;
FIG. 4B is a block diagram of a storage mechanism for Vectors of Alternates;
FIG. 4C is a block diagram of multi-segment directory table;
FIG. 5 is a block diagram of pointers relating to data fragments;
FIG. 6 is a block diagram of a storage device and its contents;
FIG. 7 is a block diagram showing the structure of a pool;
FIG. 8A is a flow diagram of a process of garbage collection;
FIG. 8B is a flow diagram of a process of writing information in a storage device;
FIG. 8C is a flow diagram of a process of synchronization;
FIG. 8D is a flow diagram of a "checkout -- read" process;
FIG. 8E is a flow diagram of a "checkout -- write" process;
FIG. 8F is a flow diagram of a "checkout -- create" process;
FIG. 9A is a flow diagram of a cache lookup process;
FIG. 9B is a flow diagram of a "checkin" process;
FIG. 9C is a flow diagram of a cache lookup process;
FIG. 9D is a flow diagram of a cache remove process;
FIG. 9E is a flow diagram of a cache read process;
FIG. 9F is a flow diagram of a cache write process;
FIG. 9G is a flow diagram of a cache update process;
FIG. 10A is a flow diagram of a process of allocating and writing objects in a storage device;
FIG. 10B is a flow diagram of a process of scaled counter updating;
FIG. 11 is a block diagram of a computer system that can be used to implement the present invention;
FIG. 12 is a flow diagram of a process of object re-validation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A method and apparatus for caching information objects is described. In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form in order to avoid unnecessarily obscuring the present invention.
Traffic Server
FIG. 2 is a block diagram of the general structure of certain elements of a proxy 30. In one embodiment, the proxy 30 is called a traffic server and comprises one or more computer programs or processes that operate on a computer workstation of the type described further below. A client 10a directs a request 50 for an object to the proxy 30 via the Internet 20. In this context, the term "object" means a network resource or any discrete element of information that is delivered from a server. Examples of objects include Web pages or documents, graphic images, files, text documents, and objects created by Web application programs during execution of the programs, or other elements stored on a server that is accessible through the Internet 20. Alternatively, the client 10a is connected to the proxy 30 through a network other than the Internet.
The incoming request 50 arrives at an input/output (I/O) core 60 of the proxy 30. The I/O core 60 functions to adjust the rate of data received or delivered by the proxy to match the data transmission speed of the link between the client 10a and the Internet 20. In a preferred embodiment, the I/O core 60 is implemented in the form of a circularly arranged set of buckets that are disposed between input buffers and output buffers that are coupled to the proxy 30 and the Internet 20. Connections among the proxy 30 and one or more clients 10a are stored in the buckets. Each bucket in the set is successively examined, and each connection in the bucket is polled. During polling, the amount of information that has accumulated in a buffer associated with the connection since the last poll is determined. Based on the amount, a period value associated with the connection is adjusted. The connection is then stored in a different bucket that is generally identified by the sum of the current bucket number and the period value. Polling continues with the next connection and the next bucket. In this way, the elapsed time between successive polls of a connection automatically adjusts to the actual operating bandwidth or data communication speed of the connection.
The I/O core 60 passes the request 50 to a protocol engine 70 that is coupled to the I/O core 60 and to a cache 80. The protocol engine 70 functions to parse the request 50 and determine what type of substantive action is embodied in the request 50. Based on information in the request 50, the protocol engine 70 provides a command to the cache 80 to carry out a particular operation. In an embodiment, the cache 80 is implemented in one or more computer programs that are accessible to the protocol engine 70 using an application programming interface (API). In this embodiment, the protocol engine decodes the request 50 and performs a function call to the API of the cache 80. The function call includes, as parameter values, information derived from the request 50.
The cache 80 is coupled to send and receive information to and from the protocol engine 70 and to interact with one or more non-volatile mass storage devices 90a-90n. In an embodiment, the storage devices 90a-90n are high-capacity, fast disk drives. The cache 80 also interacts with data tables 82 that are described in more detail herein.
Object Cache Indexing Content Indexing
In the preferred embodiment, the cache 80 stores objects on the storage devices 90a-90n. Popular objects are also replicated into a cache. In the preferred embodiment, the cache has finite size, and is stored in main memory or RAM of the proxy 30.
Objects on disk are indexed by fixed sized locators, called keys. Keys are used to index into directories that point to the location of objects on disk, and to metadata about the objects. There are two types of keys, called "name keys" and "object keys". Name keys are used to index metadata about a named object, and object keys are used to index true object content. Name keys are used to convert URLs and other information resource names into a metadata structure that contains object keys for the object data. As will be discussed subsequently, this two-level indexing structure facilitates the ability to associate multiple alternate objects with a single name, while at the same time maintaining a single copy of any object content on disk, shared between multiple different names or alternates.
Unlike other cache systems that use the name or URL of an object as the key by which the object is referenced, embodiments of the invention use a "fingerprint" of the content that makes up the object itself, to locate the object. Keys generated from the content of the indexed object are referred to herein as object keys. Specifically, the object key 56 is a unique fingerprint or compressed representation of the contents of the object 52. Preferably, a copy of the object 52 is provided as input to a hash function 54, and its output is the object key 56. For example, a file or other representation of the object 52 is provided as input to the hash function, which reads each byte of the file and generates a portion of the object key 56, until the entire file has been read. In this way, an object key 56 is generated based upon the entire contents of the object 52 rather than its name. Since the keys are content-based, and serve as indexes into tables of the cache 80, the cache is referred to as a content-indexed cache. Given a content fingerprint key, the content can easily be found.
In this embodiment, content indexing enables the cache 80 to detect duplicate objects that have different names but the same content. Such duplicates will be detected because objects having identical content will hash to the same key value even if the objects have different names.
For example, assume that the server 40 is storing, in one subdirectory, a software program comprising an executable file that is 10 megabytes in size, named "IE4.exe". Assume further that the server 40 is storing, in a different subdirectory, a copy of the same file, named "Internet Explorer.exe". The server 40 is an anonymous FTP server that can deliver copies of the files over an HTTP connection using the FTP protocol. In past approaches, when one or more clients request the two files, the cache stores a copy of each of the files in cache storage, and indexes each of the files under its name in the cache. As a result, the cache must use 20 megabytes of storage for two objects that are identical except for the name.
In embodiments of the invention, as discussed in more detail herein, for each of the objects, the cache creates a name key and an object key. The name keys are created by applying a hash function to the name of the object. The object keys are created by applying a hash function to the content of the object. As a result, for the two exemplary objects described above, two different name keys are created, but the object key is the same. When the first object is stored in the cache, its name key and object key are stored in the cache. When the second object is stored in the cache thereafter, its name key is stored in the cache. However, the cache detects the prior identical object key entry, and does not store a duplicate object key entry; instead, the cache stores a reference to the same object key entry in association with the name key, and deletes the new, redundant object. As a result, only 10 megabytes of object storage is required. Thus, the cache detects duplicate objects that have different names, and stores only one permanent copy of each such object.
FIG. 3A is a block diagram of mechanisms used to generate an object key 56 for an object 52. When client 10a requests an object 52, and the object is not found in the cache 80 using the processes described herein, the cache retrieves the object from a server and generates a object key 56 for storing the object in the cache.
Directories are the data structures that map keys to locations on disk. It is advisable to keep all or most of the contents of the directories in memory to provide for fast lookups. This requires directory entries to be small, permitting a large number of entries in a feasible amount of memory. Further, because 50% of the accesses are expected not to be stored in cache, we want to determine cache misses quickly, without expending precious disk seeks. Such fast miss optimizations dedicate scarce disk head movements to real data transfers, not unsuccessful speculative lookups. Finally, to make lookups fast via hashing search techniques, directory entries are fixed size.
Keys are carefully structured to be fixed size and small, for the reasons described earlier. Furthermore, keys are partitioned into subkeys for the purposes of storage efficiency and fast lookups. Misses can be identified quickly by detecting differences in just a small portion of keys. For this reason, instead of searching a full directory table containing complete keys, misses are filtered quickly using a table of small subkeys called a "tag table". Furthermore, statistical properties of large bit vectors can be exploited to create space-efficient keys that support large numbers of cache objects with small space requirements.
According to one embodiment, the object key 56 comprises a set subkey 58 and a tag subkey 59. The set subkey 58 and tag subkey 59 comprise a subset of the bits that make up the complete object key 56. For example, when the complete object key 56 is 128 bits in length, the subkeys 58, 59 can be 16 bits, 27 bits, or any other portion of the complete key. The subkeys 58, 59 are used in certain operations, which are described below, in which the subkeys yield results that are nearly as accurate as when the complete key is used. In this context, "accurate" means that use of the subkeys causes a hit in the cache to the correct object as often as when the complete key is used.
This accuracy property is known as "smoothness" and is a characteristic of a certain preferred subset of hash functions. An example of a hash function suitable for use in an embodiment is the MD5 hash function, which is described in detail in B. Schneier, "Applied Cryptography" (New York: John Wiley & Sons, Inc., 2d ed. 1996), at pp. 429-431 and pp. 436-441. The MD5 hash function generates a 128-bit key from an input data stream having an arbitrary length. Generally the MD5 hash function and other one-way hash functions are used in the cryptography field to generate secure keys for messages or documents that are to be transmitted over secure channels. General hashing table construction and search techniques are described in detail in D. Knuth, "The Art of Computer Programming: Vol. 3, Sorting and Searching," at 506-549 (Reading, Mass.: Addison-Wesley, 1973).
Name Indexing
Unfortunately, requests for objects typically do not identify requested objects using the object keys for the objects. Rather, requests typically identify requested objects by name. The format of the name may vary from implementation to implementation based on the environment in which the cache is used. For example, the object name may be a file system name, a network address, or a URL.
According to one aspect of the invention, the object key for a requested object is indexed under a "name key" that is generated based on the object name. Thus, retrieval of an object in response to a request is a two phase process, where a name key is used to locate the object key, and the object key is used to locate the object itself.
FIG. 3B is a block diagram of mechanisms used to generate a name key 62 based on an object name 53. According to one embodiment, the same hash function 54 that is used to generate object keys is used to generate name keys. Thus, the name keys will have the same length and smoothness characteristics of the object keys.
Similar to object key 56, the name key 62 comprises set and tag subkeys 64, 66. The subkeys 64, 66 comprise a subset of the bits that make up the complete name key 62. For example, when the complete name key 62 is 128 bits in length, the first and second subkeys 64, 66 can be 16 bits, 27 bits, or any other portion of the complete key.
Searching By Object or Name Key
Preferably, the cache 80 comprises certain data structures that are stored in the memory of a computer system or in its non-volatile storage devices, such as disks. FIG. 4 is a block diagram of the general structure of the cache 80. The cache 80 generally comprises a Tag Table 102, a Directory Table 110, an Open Directory table 130, and a set of pools 200a through 200n, coupled together using logical references as described further below.
The Tag Table 102 and the Directory Table 110 are organized as set associative hash tables. The Tag Table 102, the Directory Table 110, and the Open Directory table 130 correspond to the tables 82 shown in FIG. 2. For the purposes of explanation, it shall be assumed that an index search is being performed based on object key 56. However, the Tag Table 102 and Directory Table 110 operate in the same fashion when traversed based on a name key 62.
The Tag Table 102 is a set-associative array of sets 104a, 104b, through 104n. The tag table is designed to be small enough to fit in main memory. Its purpose is to quickly detect misses, whereby using only a small subset of the bits in the key a determination can be made that the key is not stored in the cache. The designation 104n is used to indicate that no particular number of sets is required in the Tag Table 102. As shown in the case of set 104n, each of the sets 104a-104n comprises a plurality of blocks 106.
In the preferred embodiment, the object key 56 is 128 bits in length. The set subkey 58 is used to identify and select one of the sets 104a-104n. Preferably, the set subkey 58 is approximately 18 bits in length. The tag subkey 59 is used to reference one of the entries 106 within a selected set. Preferably, the tag subkey 59 is approximately 16 bits in length, but may be as small as zero bits in cases in which there are many sets. In such cases, the tag table would be a bit vector.
The mechanism used to identify or refer to an element may vary from implementation to implementation, and may include associative references, pointers, or a combination thereof. In this context, the term "reference" indicates that one element identifies or refers to another element. A remainder subkey 56' consists of the remaining bits of the key 56. The set subkey, tag subkey, and remainder subkey are sometimes abbreviated s, t, and r, respectively.
The preferred structure of the Tag Table 102, in which each entry contains a relatively small amount of information enables the Tag Table to be stored in fast, volatile main memory such as RAM. Thus, the structure of the Tag Table 102 facilitates rapid operation of the cache. The blocks in the Directory Table 110, on the other hand, include much more information as described below, and consequently, portions of the Directory Table may reside on magnetic disk media as opposed to fast DRAM memory at any given time.
The Directory Table 110 comprises a plurality of sets 110a-110n. Each of the sets 110a-110n has a fixed size, and each comprises a plurality of blocks 112a-112n. In the preferred embodiment, there is a predetermined, constant number of sets and a predetermined, constant number of blocks in each set. As shown in the case of block 112n, each of the blocks 112a-112n stores a third, remainder subkey value 116, a disk location value 118, and a size value 120. In the preferred embodiment, the remainder subkey value 116 is a 27-bit portion of the 128-bit complete object key 56, and the comprises bits of the complete object key 56 that are disjoint from the bits that comprise the set or tag subkeys 58, 59.
In a search, the subkey values stored in the entry 106 of the Tag Table 102 matches or references one of the sets 110a-110n, as indicated by the arrow in FIG. 4 that connects the entry 106 to the set 110d. As an example, consider the 12-bit key and four-bit first and second subkeys described above. Assume that the set subkey value 1111 matches set 104n of the Tag Table 102, and the tag subkey value 0000 matches entry 106 of set 104n. The match of the tag subkey value 0000 indicates that there is a corresponding entry in set 110d of the Directory Table 110 associated with the key prefix 11110000. When one of the sets 110a-110n is selected in this manner, the blocks within the selected set are searched linearly to find a block, such as block 112a, that contains the remainder subkey value 116 that matches a corresponding portion of the object key 56. If a match is found, then there is almost always a hit in the cache. There is a small possibility of a miss if the first, second and third subkeys don't comprise the entire key. If there is a hit, the referenced object is then located based on information contained in the block, retrieved from one of the cache storage devices 90a-90n, and provided to the client 10a, as described further below.
Unlike the Tag Table, whose job is to quickly determine rule out misses with the minimal use of RAM memory, each block within Directory Table 110 includes a full pointer to a disk location. The item referenced by the disk location value 118 varies depending on the source from which the key was produced. If the key was produced based on the content of an object, as described above, then the disk location value 118 indicates the location of a stored object 124 (or a first fragment thereof), as shown in FIG. 4 in the case of block 112b. If the key is a name key, then as shown for block 112n, the disk location value 118 indicates the location of one or more Vectors of Alternates 122, each of which stores one or more object keys for the object whose name was used to generate the name key. A single Tag Table 102 and a single Directory Table 110 are shown in FIG. 4 merely by way of example. However, additional tables that provide additional levels of storage and indexing may be employed in alternate embodiments.
In the preferred arrangement, when a search of the cache is conducted, a hit or miss will occur in the Tag Table 102 very quickly. If there is a hit in the Tag Table 102, then there is a very high probability that a corresponding entry will exist in the Directory Table 110. The high probability results from the fact that a hit in the Tag Table 102 means that the cache holds an object whose full key shares X identical bits to the received key, where X is the number of bits of the concatenation of the set and tag subkeys 58 and 59. Because misses can be identified quickly, the cache 80 operates rapidly and efficiently, because hits and misses are detected quickly using the Tag Table 102 in memory without requiring the entire Directory Table 110 to reside in main memory.
When the cache is searched based on object key 56, the set subkey 58 is used to index one of the sets 104a-104n in Tag Table 102. Once the set associated with subkey 58 is identified, a linear search is performed through the elements in the set to identify an entry whose tag matches the tag subkey 59.
In a search for an object 52 requested from the cache 80 by a client 10a, when one of the sets 104a-104n is selected using the set subkey 58, a linear search of all the elements 106 in that set is carried out. The search seeks a match of the tag subkey 59 to one the entries. If a match is found, then there is a hit in the Tag Table 102 for the requested object, and the cache 80 proceeds to seek a hit in the Directory Table 110.
For purposes of example, assume that the object key is a 12-bit key having a value of 111100001010, the set subkey comprises the first four bits of the object key having a value of 1111, and the tag subkey comprises the next four bits of the object key having a value of 0000. In production use the number of remainder bits would be significantly larger than the set and tag bits to affect memory savings. The cache identifies set 15 (1111) as the set to examine in the Tag Table 102. The cache searches for an entry within that set that contains a tag 0000. If there is no such entry, then a miss occurs in the Tag Table 102. If there is such an entry, then the cache proceeds to check the remaining bits in Directory Table 110 for a match.
Multi-Level Directory Table
In one embodiment, the Directory Table 110 contains multiple sets each composed of a fixed number of elements. Each element contains the remainder tag and a disk pointer. Large caches will contain large numbers of objects, which will require large numbers of elements in the directory table. This can create tables too large to be cost-effectively stored in main memory.
For example, if a cache was configured with 128 million directory table elements, and each element was represented by a modest 8 bytes of storage, 1 GByte of memory would be requires to store the directory table, which is more memory than is common on contemporary workstation computers. Because few of these objects will be actively accessed at any time, there is a desire to migrate the underutilized entries onto disk while leaving higher utilized entries in main memory.
FIG. 4C is a diagram of a multi-level directory mechanism. The directory table 110 is partitioned into segments 111a, 111b, 111c. In the preferred embodiments, there are two or three segments 111a-111c, although a larger number of segments may be used. The first segment 111a is the smallest, and fits in main memory such as the main memory 1106 of the computer system shown in FIG. 11 and discussed in detail below. The second and third segments 111b, 111c are progressively larger. The second and third segments 111b, 111c are coupled through a paging mechanism to a mass storage device 1110 such as a disk. The second and third segments 111b, 111c dynamically page data in from the disk if requested data is not present in the main memory 1106.
As directory elements are accessed more often, the directory elements are moved to successively higher segment among the segments 111a-111c of the multi-level directory. Thus, frequently accessed directory elements are more likely to be stored in main memory 1106. The most popular elements appear in the highest and smallest segment 111a of the directory, and will all be present in main memory 1106. Popularity of entries is tracked using a small counter that is several bits in length. This counter is updated as described in the section SCALED COUNTER UPDATING. This multi-level directory approximates the performance of in-memory hash tables, while providing cost-effective aggregate storage capacity for terabyte-sized caches, by placing inactive elements on disk.
Directory Paging
As discussed, in a preferred embodiment, the Directory Table 110 is implemented as a multi-level hash table. Portions of the Directory Table may reside out of main memory, on disk. Data for the Directory Table is paged in and out of disk on demand. A preferred embodiment of this mechanism uses direct disk I/O to carefully control the timing of paging to and from disk and the amount of information that is paged.
Another embodiment of this approach exploits a feature of UNIX-type operating systems to map files directly into virtual memory segments. In this approach, the cache maps the Directory Table into virtual memory using the UNIX mmap() facility. For example, a mmap request is provided to the operating system, with a pointer to a file or disk location as a parameter. The mmap request operates as a request to map the referenced file or disk location to a memory location. Thereafter, the operating system automatically loads portions of the referenced file or disk location from disk into memory as necessary.
Further, when the memory location is updated or accessed, the memory version of the object is written back to disk as necessary. In this way, native operating system mechanisms are used to manage backup storage of the tables in non-volatile devices. However, at any given time it is typical that only a portion of the Directory Table 110 is located in main memory.
In a typical embodiment, the Directory Table and Open Directory are stored using a "striping" technique. Each set of the tables is stored on a different physical disk drive. For example, set 110a of Directory Table 110 is stored on storage device 90a, set 110b is stored on storage device 110b, etc. In this arrangement, the number of seek operations needed for a disk drive head to arrive at a set is reduced, thereby improving speed and efficiency of the cache.
It should be noted when paging data between disk and memory certain safeguards are taken to ensure that the information stored in memory is consistent with the corresponding information stored in a non-volatile storage device. The techniques used to provide efficient consistency in object caches are summarized in the context of garbage collection, in the section named SYNCHRONIZATION AND CONSISTENCY ENFORCEMENT.
Vector of Alternates
As mentioned above, it is possible for a single URL to map to an object that has numerous versions. These versions are called "alternates". In systems that do not use an object cache, versions are selected as follows. The client 10a establishes an HTTP connection to the server 40 through the Internet 20. The client provides information about itself in an HTTP message that requests an object from the server. For example, an HTTP request for an object contains header information that identifies the Web browser used by the client, the version of the browser, the language preferred by the client, and the type of media content preferred by the client. When the server 40 receives the HTTP request, it extracts the header information, and selects a variant of the object 52 based upon the values of the header information. The selected alternate is returned to the client 10a in a response message. This type of variant selection is promoted by the emerging HTTP/1.1 hypertext transfer protocol.
It is important for a cache object store to efficiently maintain copies of alternates for a URL. If a single object is always served from cache in response to any URL requests, a browser may receive content that is different than that obtained directly from a server. For this reason, each name key in the directory table 110 maps to one of the vectors of alternates 122a-122n, which enable the cache 80 to select one version of an object from among a plurality of related versions. For example, the object 52 may be a Web page and server 40 can store versions of the object in the English, French, and Japanese languages.
Each Vector of Alternates 122a-122n is a structure that stores a plurality of alternate records 123a-123n. Each of the alternate records 123a-123n is a structure that stores information that describes an alternative version of the requested object 52. For example the information describes a particular browser version, a human language in which the object has been prepared, etc. The alternate records also each store a full object key that identifies an object that contains the alternative version. In the preferred embodiment, each of the alternate records 123a-123n stores request information, response information, and an object key 56.
Because a single popular object name may map to many alternates, in one embodiment a cache composes explicit or implicit request context with the object name to reduce the number of elements in the vector. For example, the User-Agent header of a Web client request (which indicates the particular browser application) may be concatenated with a web URL to form the name key. By including contextual information directly in the key, the number of alternates in each vector is reduced, at the cost of more entries in the directory table. In practice, the particular headers and implicit context concatenated with the information object name is configurable.
These Vectors of Alternates 122a-122n support the correct processing of HTTP/1.1 negotiated content. Request and response information contained in the headers of HTTP/1.1 messages is used to determine which of the alternate records 123a-123n can be used to satisfy a particular request. When cache 80 receives requests for objects, the requests typically contain header information in addition to the name (or URL) of the desired object. As explained above, the name is used to locate the appropriate Vector of Alternates. Once the appropriate Vector of Alternates is found, the header information is used to select the appropriate alternate record for the request.
Specifically, in the cache 80, the header information is received and analyzed. The cache 80 seeks to match values found in the header information with request information of one of the alternate records 123a-123n. For example, when the cache 80 is used in the context of the World Wide Web, requests for objects are provided to a server containing the cache in the form of HTTP requests.
The cache 80 examines information in an HTTP request to determine which of the alternate records 123a-123n to use. For example, the HTTP request might contain request information indicating that the requesting client 10a is running the Netscape Navigator browser program, version 3.0, and prefers German text. Using this information, the cache 80 searches the alternate records 123a through 123n for response information that matches the browser version and the client's locale from the request information. If a match is found, then the cache retrieves the object key from the matching alternate and uses the object key to retrieve the corresponding object from the cache.
The cache optimizes the object chosen by matching the criteria specified in the client request. The client request may specify minimal acceptance criteria (e.g. the document must be a JPEG image, or the document must be Latin). The client request may also specify comparative weighting criteria for matches (e.g. will accept a GIF image with weight 0.5, but prefer a JPEG image at weight 0.75). The numeric weightings are accumulated across all constraint axes to create a final weighting that is optimized.
The object key is used to retrieve the object in the manner described above. Specifically, a subkey portion of the object key is used to initiate another search of the Tag Table 102 and the Directory Table 110, seeking a hit for the subkey value. If there is a hit in both the Tag and Directory Tables, then the block in the Directory Table arrived at using the subkey values will always reference a stored object (e.g. stored object 124). Thus, using the Vector of Alternates 122, the cache 80 can handle requests for objects having multiple versions and deliver the correct version to the requesting client 10a.
In FIG. 4, only one exemplary Vector of Alternates 122 and one exemplary stored object 124 are shown. However, in practice the cache 80 includes any number of vectors and disk blocks, depending on the number of objects that are indexed and the number of alternative versions associated with the objects.
Read Ahead
FIG. 4B is a diagram showing a storage arrangement for exemplary Vectors of Alternates 122a-122n. The system attempts to aggregate data object contiguously after the metadata. Because seeks are time-consuming but sequential reads are fast, performance is improved by consolidating data with metadata, and pre-fetching data after the metadata.
In one of the storage devices 90a-90n, each of the Vectors of Alternates 122a-122n is stored in a location that is contiguous to the stored objects 124a-124b that are associated with the alternate records 123a-123n represented in the vector. For example, a Vector of Alternates 122a stores alternate records 123a-123c. The alternate record 123a stores request and response information indicating that a stored object 124a associated with the alternate record is prepared in the English language. Another alternate record 123b stores information indicating that its associated stored object 124b is intended for use with the Microsoft Internet Explorer browser. The stored objects 124a, 124b referenced by the alternate records 123a, 123b are stored contiguously with the Vectors of alternates 122a-122n.
The Size value 120 within each alternate record indicates the total size in bytes of one of the associated Vectors of Alternates 122a-122n and the stored object 124. When the cache 80 references a Vector of Alternates 122a based on the disk location value 118, the cache reads the number of bytes indicated by the Size value. For example, in the case of the Vectors of Alternates shown in FIG. 4B, the Size value would indicate the length of the Vector of Alternate 122a plus the length of its associated stored object 124a. Accordingly, by referencing the Size value, the cache 80 reads the vector as well as the stored object. In this way, the cache 80 "reads ahead" of the Vector of Alternates 122 and retrieves all of the objects 50 from the storage devices 90a-90n. As a result, both the Vector of Alternates and the objects 50 are read from the storage device using a single seek operation by the storage device. Consequently, when there is a hit in the cache 80, in the majority of cases (where there is a single alternate) the requested object 52 is retrieved from a storage device using a single seek.
When the disk location value 118 directly references a stored object 124, rather than a Vector of Alternates 122, the Size value 120 indicates the size of the object as stored in the disk block. This value is used to facilitate single-seek retrieval of objects, as explained further herein.
The Open Directory
In one embodiment, the cache 80 further comprises an Open Directory 130. The Open Directory 130 stores a plurality of linked lists 132a-132n, which are themselves composed of a plurality of list entries 131a-131n. Each of the linked lists 132a-132n is associated with one of the sets 110a-110n in the Directory Table 110. The Open Directory 130 is stored in volatile main memory. Preferably, each list entry 131a-131n of the Open Directory 130 stores an object key that facilitates associative lookup of an information object. For example, each item within each linked list 132a-132n stores a complete object key 56 for an object 52.
The Open Directory accounts for objects that are currently undergoing transactions, to provide mutual exclusion against conflicting operations. For example, the Open Directory is useful in safeguarding against overwriting or deleting an object that is currently being read. The Open Directory also buffers changes to the Directory Table 110 before they are given permanent effect in the Directory Table 110. At an appropriate point, as discussed below, a synchronization operation is executed to move the changes reflected in the Open Directory 130 to the Directory Table 110. This prevents corruption of the Directory Table 110 in the event of an unexpected system failure or crash.
Further, in one embodiment, when an object is requested from the cache 80, the Open Directory 130 is consulted first; it is considered the most likely place to yield a hit, because it contains references to the most recently used information objects. The Open Directory in this form serves as a cache in main memory for popular data.
Disk Data Layout and Aggregation
After the Open Directory 130, Tag Table 102 and Directory Table 110 have been accessed to determine the location of a stored object 124, the object must be read from storage and transmitted to the user that requested the object. To improve the efficiency of read operations that are used to retrieve objects 50 from the cache 80, certain data aggregation techniques are used when initially storing the data. When data is initially stored on disk according to the data aggregation techniques described herein, the efficiency of subsequent reads is improved greatly.
FIG. 6 is a block diagram of a data storage arrangement for use with the cache 80 and the storage devices 90a-90n. A storage device 90a, such as a disk drive, stores data in plurality of pools 200a-200n. A pool is a segment or chunk of contiguous disk space, preferably up to 4 Gbytes in size. Pools can be allocated from pieces of files, or segments of raw disk partitions.
Each pool, such as pool 200n, comprises a header 202 and a plurality of fixed size storage spaces referred to herein as "arenas" 204a through 204n. The size of the arenas is preferably configurable or changeable to enable optimization of performance of the cache 80. In the preferred embodiment, each of the arenas 204a-204n is a block approximately 512 Kbytes to 2 Mbytes in size.
Data to be written to arenas is staged or temporarily stored or staged in a "write aggregation buffer" in memory. This buffer accumulates data, and when fall, the buffer is written contiguously, in one seek, to an arena on disk. The write aggregation buffer improves the performance of writes, and permits sector alignment of data, so data items can be directly read from raw disk devices.
The write aggregation buffer is large enough to hold the entire contents of an arena. Data is first staged and consolidated in the write aggregation buffer, before it is dropped into the (empty) arena on disk. The write aggregation buffer also contains a free top pointer that is used to allocate storage out of the aggregation buffer as it is filling, an identifier naming the arena it is covering, and a reference count for the number of active users of the arena.
Each pool header 202 stores a Magic number, a Version No. value, a No. of Arenas value, and one or more arena headers 206a-206n. The Magic number is used solely for internal consistency checks. The Version No. value stores a version number of the program or process that created the arenas 206a-206n in the pool. It is used for consistency checks to ensure that the currently executing version of the cache 80 can properly read and write the arenas. The No. of Arenas value stores a count of the number of arenas that are contained within the pool.
For each of the arenas in the pool, the pool header 202 stores information in one of the arena headers 206a-206n. Each arena header stores two one-bit values that indicate whether the corresponding arena is empty and whether the arena has become corrupted (e.g. due to physical disk surface damage, or application error).
As shown in FIG. 6 in the exemplary case of an arena 204a, each arena comprises one or more data fragments 208a-208n. Each fragment 208a-208n comprises a fragment header 208d and fragment data 208e. The fragment data 208e is the actual data for an object that is stored in the cache 80. The data for an entire stored object may reside within a single fragment, or may be stored within multiple fragments that may reside in multiple arenas. The fragment header 208d stores a Magic number value 206c, a key value 206a and a length value 206b.
The length value 206b represents the length in bytes of the fragment, including both the fragment header 208d and the fragment data 208e. The key value 206a is a copy of the object key, stored in its entirety, of the object whose data is in the fragment. Thus, the key value 206c can be used to look up the directory block that points to the first fragment that holds data of the object whose data is contained in the fragment.
According to one embodiment, the complete object key 56 is stored in association with the last fragment associated with a particular object. When an object 52 is stored in the cache 80 for the first time, the object key 56 is computed incrementally as object data is read from the originating server 40. Thus, the final value of the object key 56 cannot be known until the entire object 52 is read. The object key 56 is written at the end of the chain of fragments used to store the object, because the value of the key is not known until the last fragment is written, and because modifying existing data on disk is slow. In alternate embodiments, the fragment header can store other metadata that describes the fragment or object.
The write aggregation buffer contains a "free top pointer" 210 indicating the topmost free area of the buffer 204a. The top pointer 210 identifies the current boundary between used and available space within the buffer 204a. The top pointer 210 is stored to enable the cache 80 to determine where to write additional fragments in the buffer. Everything below (or, in FIG. 6, to the left of) the top pointer 210 contains or has already been allocated to receive valid data. The area of the arena 204a above the top pointer 210 (to the right in FIG. 6) is available for allocation for other information objects. Preferably, each fragment includes a maximum of 32 kilobytes of data. Fragments start and end on standard 512-byte boundaries of the storage device 90a. In the context of the World Wide Web, most objects are relatively small, generally less than 32K in size.
Each arena may have one of two states at a given time: the empty state or the occupied state. The current state of an arena is reflected by the Empty value stored in each arena header 206a-206n. In the occupied state, some portion of the arena is storing usable data. A list of all arenas that are currently empty or free is stored in memory. For example, main memory of the workstation that runs the cache 80 stores an array of pointers to empty arenas. In alternate embodiments, additional information can be stored in the header 206a-n of each arena. For example, the header may store values indicating the number of deleted information objects contained in the arena, and a timestamp indicating when garbage collection was carried out last on the arena.
Although three fragments are shown in FIG. 6 as an example, in practice any number of fragments may be stored in an arena until the capacity of the arena is reached. In addition, the number of pools and the number of arenas shown in FIG. 6 are merely exemplary, and any number may be used.
The above-described structure of the arenas facilitates certain consistent and secure mechanisms of updating data for objects that are stored in fragments of the arenas. FIG. 7 is a block diagram relating to updating one of the arenas 204a-204n of FIG. 6. FIG. 7 shows an arena 204a containing a first information object 208b having a header 206 and data fragments 208a-208c. Top pointer 210 points to the topmost active portion of the arena 204a, which is the end of the data segment 208c. Preferably, the Directory Table is updated only after a complete information object has been written to an arena, including header and data, and only after the top pointer of the arena has been moved successfully. For example, a complete information object is written to the arena 204a above the top pointer 210, and the top pointer is moved to indicate the new top free location of the arena. Only then is the Directory Table updated.
The delayed updating of the Directory Table is carried out to ensure that the Directory Table remains accurate even if a catastrophic system failure occurs during one of the other steps. For example, if a disk drive or other element of the system crashes before completion of one of the steps, no adverse effect occurs. In such a case, the arena 204a will contain corrupt or incomplete data, but the cache 80 will effectively ignore such data because nothing in the Directory Table 110, indexes or hash tables is referencing the corrupt data. In addition, using the Garbage Collection process described herein, the corrupt or incomplete data is eventually reclaimed.
Multi-Fragment Objects
In FIG. 3, the directory table block 112b that is arrived at based on the object key of object 52 includes a pointer directly to the fragment in which the object 52 is stored. This assumes that object 52 has been stored in a single fragment.
However, large objects may not always fit into a single fragment, for two reasons. First, fragments have a fixed maximum size (preferred value is 32 KB). Objects greater than 32 KB will be fragmented. Second, the system must pre-reserve space in the write aggregation buffer for new objects. If the object store does not know the size of the incoming object, it may guess wrong. The server may also misrepresent the true (larger) size of the object. In both cases, the object store would create a chain of fragments to handle the overflow.
Therefore, a mechanism is provided for tracking which fragments contain data from objects that are split between fragments. FIG. 5 is a block diagram of a preferred structure for keeping track of related fragments.
For the purpose of explanation, it shall be assumed that an object X is stored in three fragments 208a, 208b and 208c on storage devices 90a-90n. Using the object key for object X, the cache traverses the Tag Table to arrive at a particular block 141a within the Directory Table 110. Block 141a is the head of a chain of blocks that identify successive fragments that contain the object X. In the illustrated example, the chain is includes blocks 141a, 141b, 141c, 141d and 141e, in that order, and is formed by pointers 128a through 128d.
According to one embodiment, the head block 141a comprises a subkey value 126 and a block pointer 128a. Preferably, the subkey value 126 is 96 bits in length and comprises a subset of the value of the object key 56 for object X. The value of the block pointer 128a references the next block 141b in the chain.
Directory table block 141b comprises a fragment pointer 130a and a block pointer 128b. The fragment pointer 130a references a fragment 208a that stores the first portion of the data for the object X. The block pointer 128b of pointer block 141b references the next pointer block 141c in the chain. Like pointer block 141b, pointer block 141c has a fragment pointer 130b that references a fragment 208b. The block pointer 128c of pointer block 141c references the next pointer block 141d in the chain. Like pointer block 141c, pointer block 141d has a fragment pointer 130b that references a fragment 208c.
The object store needs a mechanism to chain fragments together. Traditional disk block chaining schemes require modifying pre-existing data on disk, to change the previous chain-link pointers to point the new next block values. Modification of pre-existing disk data is time-consuming and creates complexities relating to consistency in the face of unplanned process termination.
According to one embodiment of the invention, the need to patch new fragment pointers into extant fragments is removed by using "iterative functional pointers". Each fragment is assigned a key, and the key of the next fragment is assigned as a simple iterative function of the previous fragment's key. In this manner, fragments can be chained simply by defining the key of the next fragment, rather than by modifying the pointer of the previous fragment.
For example, the block pointer 128a is computed by applying a function to the value of subkey 126. The block pointer value 128b is computed by applying a function to the value of the block pointer 128a. The function used to compute the pointer values is not critical, and many different functions can be used. The function can be a simple accumulating function such that
key.sub.n =key.sub.n-1 +1
or the function can be a complex function such as the MD5 hash function
key.sub.n =MD5(key.sub.n-1)
The only requirement is that the range of possible key values should be sufficiently large, and the iteration should be sufficiently selected, so that the chances of range collision or cyclic looping are small. In the very unlikely event of key collision, the object will be deleted from the cache.
The last pointer block 141d in the chain has a block pointer 128d that points to a tail block 141e. The tail block 141e comprises a reference to the first block 141a in the chain. According to one embodiment, the reference contained in the tail block 141e a 96-bit subkey 132 of the object key of object X. The cache can use the 96-bit subkey 132 to locate the head block 128a of the chain. The tail block 141e, and the looped pointer arrangement it provides, enables the cache 80 to locate all blocks in a chain, starting from any block in the chain.
Three fragments 208a, 208b, and 208c are shown in FIG. 5 merely by way of example. In practice, an information object may occupy or reference any number of fragments, each of which would be identified by its own pointer block within the Directory Table 110.
When the object 52 is read from the storage device, the last fragment is read first to ensure that the content MD5 key stored there matches the directory key value. This test is done as a "sanity check" to ensure that the correct object has been located. If there is no match, a collision has occurred and an exception is raised.
Space Allocation
FIG. 10A is a flow diagram of a method of allocating space for objects newly entered into the cache and for writing such objects into the allocated space. The allocation and write method is generally indicated by reference numeral 640. Generally the steps shown in FIG. 10A are carried out when a miss has occurred in the Directory Table and Tag Table, for example, at step 898 of FIG. 8F.
Accordingly, in step 642, an information object that has been requested by a client, but not found in the cache, is looked up and retrieved from its original location. In a networked environment, the origin is a server 40, a cluster, or a disk. When the object is retrieved, in step 644 the method tests whether the object is of the type and size that can be stored in the cache, that is, whether it is "cacheable."
Examples of non-cacheable objects include Web pages that are dynamically generated by a server application, panes or portions of Web pages that are generated by client side applets, objects that are constructed based upon dynamic data taken from a database, and other non-static objects. Such objects cannot be stored in the cache because their form and contents changes each time that they are generated. If such objects were to be stored in the cache, they would be unreliable or incorrect in the event that underlying dynamic data were to change between cache accesses. The process determines whether the object is cacheable by examining information in the HTTP response from the server 40 or other source of the object.
If the object is cacheable, then in step 646 the method obtains the length of the object in bytes. For example, when the invention is applied to the World Wide Web context, the length of a Web page can be included in metadata that is carried in an HTTP transaction. In such a case, the cache extracts the length of the information object from the response information in the HTTP message that contains the information object. If the length is not present, and estimate is generated. Estimates may be incorrect, and will lead to fragmented objects.
As shown in block 648, space is allocated in a memory-resident write aggregation buffer, and the object to be written is streamed into the allocated buffer location. In a preferred embodiment, block 648 involves allocating space in a write aggregation buffer that has sufficient space and is available to hold the object. In block 650, the cache tests whether the write aggregation buffer has remaining free space. If so, the allocation and write process is complete and the cache 80 can carry out other tasks. When the write aggregation buffer becomes full, then the test of block 650 is affirmative, and control is transferred to block 656.
In block 656, the cache writes the aggregation buffer to the arena it is shadowing. In step 660, the Directory is updated to reflect the location of the new information object.
The foregoing sequence of steps is ordered in a way that ensures the integrity of information objects that are written to the cache. For example, the Directory is updated only after a complete information object has been written to an arena, including header and data. For example, if a disk drive or other element of the system crashes before completion of step 652 or step 658, no adverse effect occurs. In such a case, the arena will contain corrupt or incomplete data, but the cache will effectively ignore such data because nothing in the indexes or hash tables is referencing the corrupt data. In addition, using the garbage collection process described herein, the corrupt or incomplete data is eventually reclaimed.
Garbage Collection
FIG. 8A is a flow diagram of a method of garbage collection that can be used with the cache 80. FIG. 8B is a flow diagram of further steps in the method of FIG. 8A, and will be discussed in conjunction with FIG. 8A. Preferably, the garbage collection method is implemented as an independent process that runs in parallel with other processes that relate to the cache. This enables the garbage collection method to periodically clean up cache storage areas without interrupting or affecting the operation of the cache.
1. General Process
In the preferred embodiment, "garbage collection" generally means a process of scanning target arenas, identifying active fragments or determining whether to delete fragments, writing the active fragments contiguously to new arenas, and updating the Directory Table to reference the new locations of the fragments. Thus, in a very broad sense the method is of the "evacuation" type, in which old or unnecessary fragments are deleted and active fragments are written elsewhere, so that at the conclusion of garbage collection operations on a particular arena, the arena is empty. Preferably, both the target arenas and the new arenas are stored and manipulated in volatile memory. When garbage collection is complete, the changes carried out in garbage collection are written to corresponding arenas stored in non-volatile storage such as disk, in a process called synchronization.
In step 802, one of the pools 200a-200n is selected for garbage collection operations. Preferably, for each pool 200a-200n of a storage device 90a, the cache stores or can access a value indicating the amount of disk space in a pool that is currently storing active data. The cache also stores constant "low water mark" and "high water mark" values, as indicated by block 803. When the amount of active storage in a particular pool becomes greater than the "high water mark" value, garbage collection is initiated and carried out repeatedly until the amount of active storage in the pool falls below the "low water mark" value. The "low water mark" value is selected to be greater than zero, and the "high water mark" value is chosen to be approximately 20% less than the total storage capacity of the pool. In this way, garbage collection is carried out at a time before the pool overflows or the capacity of the storage device 90a is exceeded.
2. Usage-Aware Garbage Collection
In step 804, one of the arenas is selected as a target for carrying out garbage collection. The arena is selected by a selection algorithm that considers various factors. As indicated by block 805, the factors include, for example, whether the arena is the last arena accessed by the cache 80, and the total number of accesses to the arena. In alternate embodiments, the factors may also include the number of information objects that have been deleted from each arena, how recently an arena has been used, how recently garbage collection was previously carried out on each arena, and whether an arena currently has read or write locks set on it. Once the arena is selected for garbage collection, all of the fragments inside the object are separately considered for garbage collection.
In step 806, one of the fragments within the selected arena is selected for garbage collection. In determining which fragment or fragments to select, the cache 80 takes into account several selection factors, as indicated by block 807. In the preferred embodiment, the factors include: the time of the last access to the fragment; the number of hits that have occurred to an object that has data in the fragment; the time required to download data from the fragment to a client; and the size of the object of which the fragment is a part. Other factors are considered in alternate embodiments. Values for these factors are stored in a block 112a-112n that is associated with the object for which the fragment stores data.
In block 808, the cache determines whether a fragment should be deleted. In the preferred embodiment, block 808 involves evaluation of certain performance factors and optimization considerations.
Caches are used for two primary, and potentially conflicting, reasons. The first reason is improving client performance. To improve client performance, it is desirable for a garbage collector to retain objects that minimize server download time. This tends to bias a garbage collector toward caching documents that have been received from slow external servers. The second reason is minimizing server network traffic. To minimize server traffic, it is desirable for a garbage collector to retain objects that are large. Often, these optimizations conflict.
By storing values that identify the time required to download an object, the size of the object, and the number of times the object was hit in cache, the garbage collector can estimate, for each object, how much server download time was avoided and how much server traffic was disabled, by serving the cached copy as opposed to fetching from the original server. This metric measures the inherent "value" of the cached object.
The cache administrator then configures a parameter between 0 and 1, indicating the degree to which the cache should optimize for time savings or for traffic savings. The foregoing values are evaluated with respect to other objects in the arena, with respect to the amount of space the object is consuming, and with respect to objects recently subjected to garbage collection. Based on such evaluation, the cache 80 determines whether to delete the fragment, as shown in step 808.
If the fragment is to be deleted, then in step 812 it is deleted from the arena by marking it as deleted and overwriting the data in the fragment. When an object 52 is stored in multiple fragments, and the garbage collection process determines that one of the fragments is to be deleted, then the process deletes all fragments associated with the object. This may involve following a chain of fragments, of the type shown in FIG. 5, to another arena or even another pool.
If the fragment is not to be deleted, then in step 810 the fragment is written to a new arena. FIG. 8B, which is discussed below, shows preferred sub-steps involved in carrying out step 810.
After the fragment is deleted or moved to another arena, in step 814 the Directory Table 110 is updated to reflect the new location of the fragment. Step 814 involves using the value of the key 206a in the fragment header 208d associated with a fragment 208n to be updated to look up a block 112a-112n that is associated with the fragment. When the correct Directory Table block 112a-112n is identified, the disk location value 118 in the block is updated to reflect the new location of the fragment. If the fragment has been deleted, then any corresponding Directory Table entries are deleted.
Step 816 indicates that the method is complete after the Directory Table 110 is updated. However, it should be understood that the steps of FIG. 8A are carried out for all pools, all arenas within each pool, and all fragments within each arena.
3. Writing Fragments to New Arenas
FIG. 8B is a flow diagram of steps involved in carrying out step 810, namely, writing a fragment that is to be preserved to a new arena. The process of writing evacuated fragments to new arenas is completely analogous to writing original fragments. The data is written into a write aggregation buffer, and dropped to disk arenas when full.
In step 590, the directory tables are updated to reflect the change in location of the fragment. In the preferred embodiment, step 590 involves writing update information in the Open Directory 130 rather than directly into the Directory Table 110. At a latertime, when the process can verify that the fragment data 208e has been successfully written to one of the storage devices 90a-90n, then the changes reflected in the Open Directory 130 are written into or synchronized with the Directory Table 110.
This process is used to ensure that the integrity of the Directory Table 110 is always preserved. As noted above, buffered storage is used for the fragments; thus, when a fragment is updated or a new fragment is written, the fragment data is written to a buffer and then committed to a disk or other storage device at a future time. Thus, during garbage collection, it is possible that a fragment that has been moved to a new arena is not actually written on one of the storage devices when the garbage collection process is ready to update the Directory Table. Therefore, information about the change is stored in the Open Directory 130 until the change is committed to disk.
In step 592, the original arena is examined to test whether it has other fragments that might need to be reclaimed or moved to a new arena. If other objects are present, then control returns to step 806 of FIG. 8A, so that the next object can be processed. If no other objects are present in the current arena, then in step 594, the top pointer of the current arena is reset.
4. Buffering
In the preferred embodiment, read and write operations carried out by the cache 80 and the garbage collection process are buffered in two ways.
First, communications between the cache 80 and a client 10a that is requesting an object from the browser are buffered through a flow-controlling, streaming, buffering data structure called a VConnection. In the preferred embodiment, the cache 80 is implemented in a set of computer programs prepared in an object-oriented programming language. In this embodiment, the VConnection is an object declared by one of the programs, and the VConnection encapsulates a buffer in memory. Preferably, the buffer is a FIFO buffer that is 32 Kbytes in size.
When a client 10a-10c connects to the cache 80, the cache assigns the client to a VConnection. Data received from the client 10a is passed to the cache 80 through the VConnection, and when the cache needs to send information to the client 10a, the cache writes the information to the VConnection. The VConnection regulates the flow of data from the cache 80 to match the data transmission speed used by the client 10a to communicate with the cache. In this way, use of the VConnection avoids an unnecessary waste of main memory storage. Such waste would arise if an object being sent to the client 10a was copied to memory in its entirety, and then sent to the client; during transmission to a slow client, main memory would be tied up unnecessarily. Buffered I/O using these mechanisms tends to reduce the number of sequential read and write operations that are carried out on a disk.
5. Synchronization and Consistency Enforcement
Regularly during the garbage collection process and during operation of the cache 80, a synchronization process is carried out. The synchronization process commits changes reflected in the Open Directory 130 to the Directory Table 110 and to stable storage, such as non-volatile storage in one or more of the storage devices 90a-90n. The goal is to maintain the consistency of the data on disk at all times. That is, at any given instant the state of the data structures on disk is 100% consistent and the cache can start up without requiring checking. This is accomplished through careful ordering of the writing and synchronization of data and meta-data to the disk.
For the purposes of discussion, in this section, `data` refers to the actual objects the cache is being asked to store. For instance, if the cache is storing an HTML document, the data is the document itself. `Meta-data` refers to the additional information the cache needs to store in order to index the `data` so that it can be found during a subsequent lookup() operation as well as the information it needs to allocate space for the `data`. The `meta-data` comprises the directory and the pool headers. The directory is the index the cache uses for associating a key (a name) with a particular location on disk (the data). The cache uses the pool headers to keep track of what disk space has been allocated within the cache.
The cache uses two rules to maintain the consistency of the data structures on disk. The first rule is that meta-data is always written down after the data it points to. The rationale for the first rule is that the cache has no "permanent" knowledge of an object being in the cache until the meta-data is written. If the cache were to write down the meta-data before the data and then crash, the meta-data would associate an object name with invalid object data on disk. This is undesirable, since the cache would then have to use heuristics to try and determine which meta-data points to good data and which points to bad.
The second rule is that a pool arena cannot be marked as empty in the pool header until all the directory meta-data that points to the arena has been deleted and written to disk. This is necessary so that a crash cannot cause an empty arena to exist for which directory meta-data points to it. The problem this can cause is that the empty arena can become filled with new data, since it is empty and therefore it is available for new data to be written into it. However, "old" directory meta-data points to the same location as the new data. It is possible for accesses to the old directory meta-data to return the new data instead of either returning the old data or failing.
FIG. 8C is a flow diagram of a preferred synchronization method 820 that implements the foregoing two rules. In block 822, an object is written to the cache. Block 822 involves the steps of block 824 and block 826, namely, creating metadata in the Open Directory, and writing and syncing the object data to disk.
The steps of blocks 828 through 820' are carried out periodically. As indicated in block 828, for each piece of meta-data in the open directory table, a determination is made whether the data that the metadata points to is already synchronized to disk, as shown in block 821. If so, then in block 823, the cache copies the metadata that points to the stable data from the Open Directory to the Directory Table. In block 825, the changes are synchronized to disk.
In block 827, garbage collection is carried out on an arena. Block 827 may involve the steps shown in FIG. 8A. Alternatively, garbage collection generally involves the steps shown in block 829, block 831, and block 820'. As shown in block 829, for each fragment in the arena, the cache deletes the directory metadata that points to the segment, and writes the directory metadata to disk. In block 831, the pool header is modified in memory such that the arena is marked as empty. In block 820', the pool header is written and synced to disk.
The steps that involve writing information to disk preferably use a "flush" operation provided in the operating system of the workstation that is running the cache 80. The "flush" operation writes any data in the buffers that are used to store object data to a non-volatile storage device 90a-90c.
Using the foregoing methods, the Directory Table is not updated with the changes in the Open Directory until the data that the changes describe is actually written to disk or other non-volatile storage. Also, the cache 80 postpones updating the arenas on disk until the changes undertaken by the garbage collection process are committed to disk. This ensures that the arenas continue to store valid data in the event that a system crash occurs before the Directory Table is updated from the Open Directory.
6. Re-Validation
In the preferred embodiment, the cache provides a way to re-validate old information objects in the cache so that they are not destroyed in the garbage collection process.
FIG. 12 is a flow diagram of a preferred re-validation process. In block 1202, an external program or process delivers a request to the cache that asks whether a particular information object has been loaded by a client recently. In response to the request, as shown in block 1204, the cache locates the information object in the cache. In block 1206, the cache reads a Read Counter value associated in the directory tables with the information object. In block 1208, the cache tests whether the Read Counter value is high.
If the Read Counter value is high, then the information object has been loaded recently. In that case, in block 1210 the cache sends a positive response message to the requesting process. Otherwise, as indicated in block 1212, the information object has not been loaded recently. Accordingly, as shown in block 1214, the cache sends a negative responsive message to the calling program or process. In block 1216, the cache updates an expiration date value stored in association with the information object to reflect the current date or time. By updating the expiration date, the cache ensures that the garbage collection process will not delete the object, because after the update it is not considered old. In this way, an old object is refreshed in the cache without retrieving the object from its origin, writing it in the cache, and deleting a stale copy of the object.
Scaled Counter Updating
FIG. 10B is a flow diagram of a method of scaled counter updating. In the preferred embodiment, the method of FIG. 10B is used to manage the Read Counter values that are stored in each block 112a-112n of a set of the Directory Table, as shown in FIG. 3A. However, the method of FIG. 10B is not limited to that context. The method of FIG. 10B is applicable to any application that involves management of each of a plurality of objects that has a counter, and in which it is desirable to track the most recently used or least recently used objects. A key advantage of the method of FIG. 10B in comparison to past approaches is that it enables large counter values to be tracked in a small storage area.
In the preferred embodiment, each of the Read Counter values stored in blocks 112a-112n is stored in three bit quantities. During operation of the cache 80, when a block is accessed, the Read Counter value of the block is incremented by one. The highest decimal number that can be represented by a three-bit quantity is 7. Accordingly, a Read Counter could overflow after being incremented seven times. To prevent counter overflow, while enabling the counters to track an unlimited number of operations that increment them, the method of FIG. 10B is periodically executed.
The following discussion of the steps of FIG. 10B will be more clearly understood with reference to Table 1:
TABLE 1______________________________________SUCCESSIVE COUNTER VALUES COUNTERSEVENT A B C______________________________________1: Start 1 1 12: Increment 2 1 13: Increment 7 3 14: Decrement 6 2 05: Reclaim 6 2 --______________________________________
In Table 1, the EVENT column identifies successive events affecting a set of counter values, and briefly indicates the nature of the event. The COUNTERS heading indicates three counter values A, B, and C represented in separate columns. Each of the counter values A, B, C corresponds to a counter value that is stored in a different block 112a-112n of the Directory Index 110. Thus, each row of Table 1 indicates the contents of three counter values at successive snapshots in time.
Event 1 of Table 1 represents an arbitrary starting point in time, in which the hash table entries containing the counter values A, B, C each have been accessed once. Accordingly, the value of each counter A, B, C is one. At event 2, the cache has accessed the hash table entry that stores counter value A. Accordingly, counter A has been incremented and its value is 2; the other counters B, C are unchanged. Assume that several other hash table entry accesses then occur, each of which causes one of counters A, B, or C to be incremented. Thereafter, at event 3, the values of the counters A, B, C are 7, 3, and 1 respectively. Thus, counter A is storing the maximum value it can represent, binary 111 or decimal 7, and will overflow if an attempt is made to increment it to a value greater than 7.
At this point, the method of FIG. 10B is applied to the counters A, B, C. In step 622, the value of all the counters is read. In step 624, the sum of all the counter values is taken. In the case of Table 1, the sum is given by 7+3+1=11. In step 626, the maximum sum that can be represented by all the counters is computed based upon the length in bits of the counter values. In the case of a three-bit value, the maximum value of one counter is 7 and the maximum value for the sum of three three-bit counters is 7×3=21. Alternatively, step 626 can be omitted; the maximum value can be stored as a constant that is available to the scaled counter method 620 and simply retrieved when needed.
In step 628, the method computes the value (maximum -- value/2), truncating any remainder or decimal portion, and compares it to the sum of all the counters. In the example above, the relationship is
Sum=11
Maximum -- Value=21
Maximum -- Value/2=10
(Sum>Maximum -- Value/2)=TRUE
Since the result is true, control is transferred to step 630, in which all the counter values are decremented by 1. The state of counters A, B, C after this step is shown by Event 4, "Decrement." Note that counter C, which represents the least recently used hash table entry, has been decremented to zero. At this point, least recently used hash table entries can be reclaimed or eliminated by scanning the corresponding counter values and searching for zero values. The result of this step is indicated in Event 5 of Table 1, "Reclaim." The values of counters A and B are unchanged, and the value of counter C is undefined because its corresponding hash table entry has been deleted from the hash table.
When the method of FIG. 10B is repeated periodically and regularly, none of the plurality of counter values will overflow. Also, least recently used entries are rapidly identified by a counter value of zero, and can be easily eliminated from the cache. Counter values can be maintained in few bits even when hash table entries are accessed millions of times. Thus, the method of FIG. 10B provides a fast, efficient way to eliminate least recently used entries from a list.
Cache Operations
In the preferred embodiment, the cache 80 is implemented in one or more computer programs that are accessible to external programs through an API that supports read and write operations. The read and write operations are carried out on the Open Directory 130, which is the only structure of the cache 80 that is "visible" to external programs or processes. The read operation is invoked by an external program that wants to locate an object in the cache. The write operation is invoked by a program that wants to store an object in the cache. Within the programs that make up the cache 80, operations called lookup, remove, checkout, and checkin are supported. The lookup operation looks up an object in the Open Directory based upon a key. The remove operation removes an object from the Open Directory based upon a key. The checkout operation obtains a copy of a block from the Directory Table 110 in an orderly manner so as to ensure data consistency. The checkin operation returns a copy of a block (which may have been modified in other operations) to the Directory Table 110. In other embodiments, a single cache lookup operation combines aspects of these operations.
1. Lookup
In an alternate embodiment, a LOOKUP operation is used to determine whether a particular object identified by a particular name is currently stored in the cache 80. FIG. 9A is a flow diagram of steps carried out in one embodiment of the LOOKUP operation, which is generally designated by reference numeral 902. The LOOKUP operation is initiated by a command from the protocol engine 70 to the cache 80 when a request message from a client 10a seeks to retrieve a particular object from the server 40. The request message from the client 10a identifies the requested object by its name.
When the process is applied in the context of the World Wide Web, the name is a Uniform Resource Locator (URL). In step 904, the cache 80 converts the name of the object to a key value. In the preferred embodiment, the conversion step is carried out as shown in FIG. 3B. The object name 53 or URL is passed to a hash function, such as the MD5 one-way has function. The output of the hash function is an object name key 62. The object name key 62 can be broken up into one or more subkey values 64, 66.
In step 906, the cache 80 looks up the request key value in the Open Directory 130. The Open Directory is consulted first because it is expected to store the most recently requested objects and therefore is likely to contain the object in the client request. Preferably, step 906 involves using one of the subkey values as a lookup key. For example, a 17-bit or 18-bit subkey value can be used for the lookup.
In step 908, the cache 80 tests whether the subkey value has been found in the Open Directory. If the subkey value has been found in the Open Directory, then in step 910 the cache 80 retrieves the object from one of the storage devices, and delivers the object to the client. The retrieval sub-step involves the sub-steps described above in connection with locating objects in pools, arenas, and fragments of non-volatile storage in the storage devices 90a-90c. The delivery sub-step involves constructing an HTTP response to the client that includes data of the object, opening an HTTP connection to the client, and sending the HTTP request to the client.
If the subkey value is not found in the Open Directory, then in step 912, the cache 80 looks up the request subkey value in the Tag Table 102. In step 914, the cache 80 tests whether the subkey value was found in the Tag Table 102. If no match was found, then in step 916 the cache 80 stores information about the fact that no match occurred, for later use as described below. The information can be a bit indicating that a miss in the Tag Table 102 occurred.
In step 918, the cache 80 looks up the subkey value in the Directory Table. If the test of step 914 was affirmative, then the cache 80 retrieves a subkey value matching the request subkey value from one of the entries 106 of the tag Table 102. Its value is used as a key to look up the request key value in the Directory Table. In step 920, the cache 80 tests whether the request key value was found in the Directory Table. If a hit occurs, and there was a miss in the Tag Table as indicated by the information stored in step 916, then in step 922 the cache 80 updates the Open Directory with information related to the Directory Table hit. Control is then passed to step 910 in which the object is obtained and delivered to the client in the manner described above.
If the test of step 920 is negative, then the requested object is not in the cache, and a cache miss condition occurs, as indicated in step 924. In response to the miss condition, in step 926 the cache 80 obtains a copy of the requested object from the server that is its source. For example, in the Web context, the cache 80 opens an HTTP connection to the URL provided in the client's request, and downloads the object. The object is then provided to the client and stored in the cache for future reference.
In a preferred embodiment, the LOOKUP operation is implemented as a method of an object in an object-oriented programming language that receives a key value as a parameter.
2. Cache Open Read Process
FIG. 9E is a flow diagram of a preferred process of reading an object that is identified by an object name (such as a URL) from the cache. In the preferred embodiment, the process of FIG. 9E is called "open -- read," and represents the sole external interface of the cache 80. It is advantageous, to ensure control and consistency of data in the cache, to enable external programs to access only operations that use or modify the Open Directory 130. Preferably, the process of FIG. 9E is implemented as a program or programmatic object that receives an object name, and information about the user's particular request, as input parameters. The read process returns a copy of an object associated with a key that is found in the cache using the lookup process. Thus, the read process, and other processes that are invoked or called by it, are an alternative to the LOOKUP operation described above in connection with FIG. 9A.
In step 964, the process checks out a Vector of Alternates so that alternates in the vector can be read. Preferably, step 964 involves invoking the checkout -- read process described herein in connection with FIG. 8D, providing a key derived from the object name as a parameter. Checking out a vector involves checking out a block from the Open Directory that has a pointer to the vector, and reaching the block from the cache.
If the checkout operation is successful, then in step 966 the process uses the request information to select one of the alternates from among the alternates in the vector. This selection is carried out in the manner described above in connection with the Vector of Alternates 122. In an embodiment, the selection operation is carried out by another program or programmatic object that returns a success/failure indication depending upon whether a suitable alternate is located. If the selection is successful, then in step 968 the process checks the Vector of Alternates back in. In step 970, the process reads the object that is pointed to by the selected alternate.
If step 964 or step 966 results in failure, then the requested document does not exist in the cache. Accordingly, in step 972 the process returns a "no document" error message to the calling program or process.
3. Cache Open Write Process
FIG. 9F is a flow diagram of a process of writing an object into the cache. As in the case of the read process described above in connection with FIG. 9E, the write process preferably is implemented as an "open -- write" method that is the sole interface of the cache 80 to external programs needing to store objects in the cache. Preferably, the process of FIG. 9F is implemented as a program or method that receives an object name, request information, and response information as input parameters. The object name identifies an object to be written into the cache; in the preferred embodiment, the object name is a name key 62 derived from a URL using the mechanism shown in FIG. 3B.
The write process is initiated when a client 10a has requested an object 52 from the cache 80 that is not found in the cache. As a result, the cache 80 opens an HTTP transaction with the server 40 that stores the object, and obtains a copy of the object from it. The request information that is provided to the cache write process is derived from the HTTP request that came from the client. The response information is derived from the response of the server 40 to the cache 80 that supplies the copy of the object.
In step 974, the process checks out a Vector of Alternates. This step involves computing a key value based upon the object name, looking up a set and a block in the Open Directory that map to the key value, and locating a Vector of Alternates, if any, that corresponds to the block. If no vector exists, as shown in step 984, a new vector is created
If a vector is successfully checked out or created, then in step 976 the process uses the request information to define a new alternate record 123a-123n within the current alternate. The new alternate record references the location of the object, and contains a copy of the request information and the response information. The new alternate is added to the Vector of Alternates. Duplicate alternate records are permitted; the Vector of Alternates can contain more than one alternate record that contains the same request and response information. Testing existing alternate records to identify duplicates is considered unnecessary because only a small incremental amount of storage is occupied by duplicate alternate records.
In step 978, the modified vector is checked into the cache using the steps described above. In step 980, the object is written to one of the data storage devices 90a-90c in the manner described above, using the key value. If the key is found to be in use during step 980, then the write operation fails. This avoids overwriting an object identified by a key that is being updated.
4. Cache Update Process
FIG. 9G is a flow diagram of a cache update process. The update process is used to modify a Vector of Alternates to store different request information or response information. Generally, the update process is invoked by the protocol engine 70 when the cache 80 is currently storing an object 52 that matches a request from a client 10a, but the protocol engine determines that the object has expired or is no longer valid. Under these circumstances, the protocol engine 70 opens an HTTP transaction to the server 40 that provided the original object 52, and sends a message that asks the server whether the object has changed on the server. This process is called "revalidation" of the object 52. If the server 40 responds in the negative, the server will provide a short HTTP message with a header indicating that no change has occurred, and providing new response information. In that case, the protocol engine 70 invokes the cache update process in order to move the new response information about the object 52 into the cache 80.
If the server 40 responds affirmatively that the object 52 has changed since its expiration date or time in the cache 80, then the update process is not invoked. Instead, the server 40 returns a copy of the updated object 52 along with a new expiration date and other response information. In that case, the protocol engine 70 invokes the cache write process and the create processes described above to add the new object 52 to the cache 80.
As shown in FIG. 9G, the update process receives input parameters including an object name, an "old" identifier, request information, and response information. The object name is a URL or a key derived from a URL. The request information and response information are derived from the client's HTTP request for the object 52 from the cache 80, and from the response of the server 40 when the cache obtains an updated copy of the object from the cache.
The "old" identifier is a value that uniquely identifies a pair of request information and response information. In the preferred embodiment, when a cache miss causes the cache 80 to write a new object into the cache, information from the client request is paired with response information from the server that provides a copy of the object. Each pair is given a unique identifier value.
In step 986, the process checks out a Vector of Alternates corresponding to the object name from the cache. Preferably, this is accomplished by invoking the checkout -- write process described herein. This involves using the object name or URL to look up an object in the Open Directory, the Tag Table, and the Directory Index, so that a corresponding Vector of Alternates is obtained. If the checkout step fails, then in step 996 the process returns an appropriate error message.
If the checkout is successful, then in step 988 a copy or clone of the vector is created in main memory. A request/response identifier value is located within the vector by matching it to the Old Identifier value received as input to the process. The old identifier value is removed and a new identifier is written in its place. The new identifier uniquely identifies the new request and response information that is provided to the process as input.
In step 990, the new vector is written to one of the storage devices 90a-90c, and in step 992 the new vector is checked in to the cache. In carrying out these steps, it is desirable to completely write the clone vector to the storage device before the vector is checked in. This ensures that the writing operation is successful before the directory tables are modified to reference the clone vector. It also ensures that the old vector is available to any process or program that needs to access it.
5. Directory Lookup
FIG. 9C is a flow diagram of a preferred embodiment of a process of looking up information in the Open Directory 130. The process of FIG. 9C is implemented as a program process or method that receives a subkey portion of a name key 62 as an input parameter. In preceding steps that are not shown, it will be understood that the protocol engine 70 receives an object name, such as a URL. For example, a URL is provided in an HTTP request issued by a client to a server that is operating the cache. The protocol engine 70 applies a hash function to the object name. The hash function yields, as its result or output, a name key that identifies a set in the cache.
In step 948, the process attempts to check out one or more blocks that are identified by the subkey from the Directory Index. The block checkout step preferably involves invoking the checkout -- read process described herein. Thus,
If the checkout attempt results in a failure state, then in step 950 the process returns an error message to the program or process that called it, indicating that a block matching the input subkey was not found in the cache. Control is passed to step 952 in which the process concludes.
If the checkout attempt is successful, then a copy of a block becomes available for use by the calling program. In step 954, the block that was checked out is checked in again. In step 956, the process returns a message to the calling program indicating that the requested block was found. Processing concludes at step 952.
Thus, a cache search operation involves calling more primitive processes that seek to check out a block identified by a key from the Open Directory. If the primitives do not find the block in the Open Directory, the Directory Index is searched.
When a block is found, it is delivered to the client. For example, when the invention is applied to the World Wide Web context, the data block is delivered by opening an HTTP connection to the client and transmitting the data block to the client using an HTTP transaction. This step may involve buffering several data blocks before the transaction is opened.
6. Cache Remove Process
FIG. 9D is a flow diagram of a process of removing a block relating to an object from the cache. As in the case of the checkout operations, the cache remove process receives a key value as input. The process comprises steps 958 to 962. These steps carry out operations that are substantially similar to the operations of steps 948, 954, and 952 of FIG. 9C. To accomplish removal of a block found in the cache, however, in step 960 the process sets the deletion flag, and checks the block in with the deletion flag set. As described herein in connection with the check-in process (steps 938 and 944 of FIG. 9B), when the deletion flag is set, the block will be marked as deleted. Thereafter, the block is eventually removed from the Directory Index when the changes reflected in the Open Directory are synchronized to the Directory Index.
7. Checkout Read Operation
FIG. 8D is a flow diagram of a checkout -- read operation that is used in connection with the Directory Table 110. The checkout -- read operation is used to obtain a copy of a block from the Directory Table 110 that matches a particular key. Once the block is checked out from the Directory Table 110, the block can be read and used by the process that checked it out, but by no other process. Thereafter, to make the block available to other processes, the block is checked back in. Complementary checkout check-in processes are used in order to ensure that only one process at a time can modify a Directory Table block, a mechanism that is essential to ensure that the Directory Table always stores accurate information about objects in the cache. Thus, it will be apparent that the checkout and check-in processes is a primitive process that assists in searching the cache for a particular object.
As indicated in FIG. 8D, the checkout -- read operation receives a key value as input. In the preferred embodiment, the input key value is a subkey portion of a name key 62 that corresponds to an object name.
Because the object store will be modifying portions of memory and disk data structures, it needs to guarantee a brief period of mutual exclusion to a subset of the cache data structures in order to achieve consistent results. The cache data structures are partitioned into 256 virtual "slices", selected by 8 bits of the key. Each slice has an associate mutex lock. In step 832, the process seeks to obtain the lock for the input key. If a lock cannot be obtained, the process waits the brief time until it becomes available. A lock can be unavailable if another transaction is modifying the small about of memory state associated with a key that falls in the same slice.
When a lock is obtained, the input key becomes unavailable for use by other processes. In step 834, the process determines which set 110a-110n of the Directory Table 110 corresponds to the key. The process then locates one of the block lists 132a, 132b of the Open Directory 130 that corresponds to the set of the Directory Table 110, by associating the value of a subkey of the input key with one of the block lists. In step 836, the process scans the blocks in the selected block list of the Open Directory 130, seeking a match of the input key to a key stored in one of the blocks.
If a match is found, then in step 838 the process tests whether the matching block is currently in the process of being created or destroyed by another process. If the matching block is currently in the process of being created or destroyed, then in step 840 an error message is returned to the protocol engine 70 indicating that the current block is not available.
On the other hand, if the matching block is not currently in the process of being created or destroyed, then the block can be used. Accordingly, in step 842 the process increments a read counter. The read counter is an internal variable, associated with the block, that indicates the number of processes or instances of programmatic objects that are reading the block. Such processes or objects are called "readers." In step 844, the process obtains a copy of the block, and returns it to the calling program or process.
If a match is not found in the scan of step 836, then in step 846, the process invokes a search of the Directory Table, seeking a match of the key to a set and block of the Directory Table using a process that is described further herein. If no match of the key is found in the search, then in step 848 the process returns an error message to the calling program or process, indicating that the requested object does not exist in the cache. Although the specific response to such a message is determined by the calling program or process, in the World Wide Web context, generally the proxy 30 contacts the server 40 that stores the object using an HTTP request, and obtains a copy of the requested object.
If a match is found during the Directory Index lookup of step 846, then in step 850 a corresponding block is added to the Open Directory. This is carried out by creating a new Open Directory block in main memory; initializing the block by copying information from the corresponding Directory Index block; and adding a reference to the new block to the corresponding list of blocks 132a, 132b.
8. Checkout Write Operation
FIG. 8E is a flow diagram of a checkout -- write process or operation that is used in connection with the Open Directory 130. The checkout -- write operation is used to obtain a copy of a block from the Open Directory 130 that matches a key that is passed to the process, for the purpose of modifying or updating the contents of the block, or an object or vector that is associated with the block. Once a block is checked out of the Open Directory 130 using checkout -- write, other processes can modify the block or its associated object or vector. The block is then checked back in using the checkin process described herein. Using these operations, changes are stored in the Open Directory and then propagated to the Directory Table in an orderly manner.
As indicated in FIG. 8E, the checkout -- write process receives a key value as input. In the preferred embodiment, the input key value is a subkey portion of a name key 62 that corresponds to an object name. In step 854, the process seeks to obtain a lock on the designated key. If a lock cannot be obtained, the process waits until one is available.
When a lock is obtained, the key becomes unavailable for use by other processes. In step 856, the process determines which set 110a-110n of the Directory Table 110 corresponds to the key. The process then locates one of the block lists 132a, 132b of the Open Directory 130 that corresponds to the set of the Directory Table 110. In step 858, the process scans the blocks in the selected block list of the Open Directory 130, seeking a match of the input key to a key stored in one of the blocks.
If a match is found, then in step 864 the process tests whether the matching block is currently in the process of being created or destroyed by another process. If so, then in step 866 an error message is returned to the protocol engine 70 or cache 80 indicating that the current block is not available. If the matching block is not currently in the process of being created or destroyed, then the block can be used. Accordingly, in step 868 the process increments a write counter. The write counter is an internal variable, stored in association with the block, that indicates the number of processes or programmatic objects that are writing the block. In step 870, the process obtains a copy of the block, returns it to the calling program or process, and also marks the copy as being modified. The marking ensures that any changes made to the block will be reflected in the Directory Index when the Open Directory is synchronized to the Directory Index.
If a match is not found in the scan of step 858, then in step 860, the process invokes a search of the Directory Index using a process that is described further herein. If no match is found in the search, then in step 862 the process returns an error message to the calling program or process, indicating that the requested object does not exist in the cache. In the World Wide Web context, typically the calling program would contact the originating server that stores the object using an HTTP request, and obtain a copy of the requested object.
If a match is found during the Directory Index lookup of step 860, then in step 874 a corresponding block is added to the Open Directory. This is carried out by creating a new Open Directory block in main memory; initializing the block by copying information from the corresponding Directory Index block; and adding a reference to the new block to the corresponding list of blocks 132a, 132b. Control is then passed to step 868, in which the write count is incremented and the process continues as described above in connection with steps 868-870.
9. Checkout Create Operation
FIG. 8F is a flow diagram of a checkout -- create operation that is supported for use in connection with the Open Directory 130. The checkout -- create operation is used to create a new block in the Open Directory 130 for a name key that corresponds to a new object that is being added to the cache. Once the block is created in the Open Directory 130, the object can be obtained by users from the cache through the Open Directory 130.
As indicated in FIG. 8F, the checkout -- create process receives a key value as input. In the preferred embodiment, the input key value is a subkey portion of a name key 62 that corresponds to an object name. In step 876, the process seeks to obtain a lock on the designated key. If a lock cannot be obtained, the process waits until one is available.
When a lock is obtained, the key becomes unavailable for use by other processes. In step 878, the process determines which set 110a-110n of the Directory Table 110 corresponds to the key. The process then locates the set of the Open Directory 130 that corresponds to the set of the Directory Table 110, using the set subkey bits of the input key. In step 880, the process scans the blocks in the selected block list of the Open Directory 130, seeking a match of the input key to a key stored in one of the blocks.
If a match is found, then an attempt is being made to create a block that already exists. Accordingly, in step 882 the process tests whether the matching block has been marked as deleted, and currently has no other processes reading it or writing it. If the values of both the reader counter and the writer counter are zero, then the block has no other processes reading it or writing it. If the values of either the reader counter or the writer counter are nonzero, or if the matching block has not been marked as deleted, then the block is a valid previously existing block that cannot be created. In step 884 an error message is returned to the protocol engine 70 or cache 80 indicating that the current block is not available to be created.
If the matching block is deleted and has no writers or readers accessing it, then the process can effectively create a new block by clearing and initializing the matching, previously created block. Accordingly, in step 886 the process clears the matching block. In step 888 the process initializes the cleared block by zeroing out particular fields and setting the block's key value to the key. In block 890, the process increments the writer counter associated with the block, and marks the block as created. In step 892, the process returns a copy of the block to the calling process or programmatic object, and marks the block as being modified.
If a match is not found in the scan of step 880, then no matching block currently exists in the Open Directory 130. In step 894, the process carries out a search of the Directory Index using a process that is described further herein. If a match occurs, then in step 896, the process returns an error message to the calling program or process, indicating that the block to be created already exists in the cache and cannot be deleted.
If no match is found in the search, then no matching block currently exists in the entire cache. In step 898, the process creates a new Open Directory block, and adds a reference to that block to the list 132a, 132b associated with the set value computed in step 878. Control is passed to step 890, in which the processing continues as described above in connection with steps 890-892.
10. Checkin Process
FIG. 9B is a flow diagram of a block check-in process. The cache 80 carries out the process of FIG. 9B to check a block into the Open Directory 130 after the block is read, modified, or deleted. In an embodiment, the process of FIG. 9B is implemented as a program process or object that receives an identifier of a block as a parameter. Because the key is present in the checked out block, we do not need to pass in the key as an argument.
In step 930, the process attempts to get a lock for the key associated with the block. If no lock is available, then the process enters a wait loop until a lock is available. When a lock is available, in step 932 the process tests whether the block is being checked in after the block has been modified. If so, then in step 934 the writer count for the block is decremented, indicating that a process has completed writing the block.
In step 936, the process tests whether the check-in process has been carried out successfully. If this test is affirmative, then in step 942 the process copies the information in the current block to the corresponding original block in the Open Directory. In this way, the Open Directory is updated with any changes that were carried out by the process that modified the copy of the block that was obtained in the checkout process. Thereafter, and if the test of step 936 is negative, the process tests whether a delete check-in flag is set. The delete check-in flag indicates that the block is to be deleted after check-in. The delete flag is an argument to the checkin operation. If the flag is set, then in step 944 the process marks the block as deleted. Processing concludes at step 940.
If the test of step 932 is negative, then the block is not being modified. As a result, the only other possible state is that the block has been read. Accordingly, in step 946, the reader count is decremented.
Implementation of Methods
In the preferred embodiment, the methods described herein are carried out using a general-purpose programmable digital computer system of the type illustrated in FIG. 11. Each of the methods can be implemented in several different ways. For example, the methods can be implemented in the form of procedural computer programs, object-oriented programs, processes, applets, etc., in either a single-process or multi-threaded, multi-processing system.
In a preferred embodiment, each of the processes is independent and re-entrant, so that each process can be instantiated multiple times when the cache is in operation. For example, the garbage collection process runs concurrently with and independent of the allocation and writing processes.
Hardware Overview
FIG. 11 is a block diagram that illustrates a computer system 1100 upon which an embodiment of the invention may be implemented. Computer system 1100 includes a bus 1102 or other communication mechanism for communicating information, and a processor 1104 coupled with bus 1102 for processing information. Computer system 1100 also includes a main memory 1106, such as a random access memory (RAM) or other dynamic storage device, coupled to bus 1102 for storing information and instructions to be executed by processor 1104. Main memory 1106 also may be used for storing temporary variables or other intermediate information during execution of instructions to be executed by processor 1104. Computer system 1100 further includes a read only memory (ROM) 1108 or other static storage device coupled to bus 1102 for storing static information and instructions for processor 1104. A storage device 1110, such as a magnetic disk or optical disk, is provided and coupled to bus 1102 for storing information and instructions.
Computer system 1100 may be coupled via bus 1102 to a display 1112, such as a cathode ray tube (CRT), for displaying information to a computer user. An input device 1114, including alphanumeric and other keys, is coupled to bus 1102 for communicating information and command selections to processor 1104. Another type of user input device is cursor control 1116, such as a mouse, a trackball, or cursor direction keys for communicating direction information and command selections to processor 1104 and for controlling cursor movement on display 1112. This input device typically has two degrees of freedom in two axes, a first axis (e.g., x) and a second axis (e.g., y), that allows the device to specify positions in a plane.
The invention is related to the use of computer system 1100 for caching information objects. According to one embodiment of the invention, caching information objects is provided by computer system 1100 in response to processor 1104 executing one or more sequences of one or more instructions contained in main memory 1106. Such instructions may be read into main memory 1106 from another computer-readable medium, such as storage device 1110. Execution of the sequences of instructions contained in main memory 1106 causes processor 1104 to perform the process steps described herein. In alternative embodiments, hard-wired circuitry may be used in place of or in combination with software instructions to implement the invention. Thus, embodiments of the invention are not limited to any specific combination of hardware circuitry and software.
The term "computer-readable medium" as used herein refers to any medium that participates in providing instructions to processor 1104 for execution. Such a medium may take many forms, including but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media includes, for example, optical or magnetic disks, such as storage device 1110. Volatile media includes dynamic memory, such as main memory 1106. Transmission media includes coaxial cables, copper wire and fiber optics, including the wires that comprise bus 1102. Transmission media can also take the form of acoustic or light waves, such as those generated during radio-wave and infra-red data communications.
Common forms of computer-readable media include, for example, a floppy disk, a flexible disk, hard disk, magnetic tape, or any other magnetic medium, a CD-ROM, any other optical medium, punch cards, paper tape, any other physical medium with patterns of holes, a RAM, a PROM, and EPROM, a FLASH-EPROM, any other memory chip or cartridge, a carrier wave as described hereinafter, or any other medium from which a computer can read.
Various forms of computer readable media may be involved in carrying one or more sequences of one or more instructions to processor 1104 for execution. For example, the instructions may initially be carried on a magnetic disk of a remote computer. The remote computer can load the instructions into its dynamic memory and send the instructions over a telephone line using a modem. A modem local to computer system 1100 can receive the data on the telephone line and use an infrared transmitter to convert the data to an infrared signal. An infrared detector coupled to bus 1102 can receive the data carried in the infrared signal and place the data on bus 1102. Bus 1102 carries the data to main memory 1106, from which processor 1104 retrieves and executes the instructions. The instructions received by main memory 1106 may optionally be stored on storage device 1110 either before or after execution by processor 1104.
Computer system 1100 also includes a communication interface 1118 coupled to bus 1102. Communication interface 1118 provides a two-way data communication coupling to a network link 1120 that is connected to a local network 1122. For example, communication interface 1118 may be an integrated services digital network (ISDN) card or a modem to provide a data communication connection to a corresponding type of telephone line. As another example, communication interface 1118 may be a local area network (LAN) card to provide a data communication connection to a compatible LAN. Wireless links may also be implemented. In any such implementation, communication interface 1118 sends and receives electrical, electromagnetic or optical signals that carry digital data streams representing various types of information.
Network link 1120 typically provides data communication through one or more networks to other data devices. For example, network link 1120 may provide a connection through local network 1122 to a host computer 1124 or to data equipment operated by an Internet Service Provider (USP) 1126. ISP 1126 in turn provides data communication services through the world wide packet data communication network now commonly referred to as the "Internet" 1128. Local network 1122 and Internet 1128 both use electrical, electromagnetic or optical signals that carry digital data streams. The signals through the various networks and the signals on network link 1120 and through communication interface 1118, which carry the digital data to and from computer system 1100, are exemplary forms of carrier waves transporting the information.
Computer system 1100 can send messages and receive data, including program code, through the network(s), network link 1120 and communication interface 1118. In the Internet example, a server 1130 might transmit a requested code for an application program through Internet 1128, ISP 1126, local network 1122 and communication interface 1118. In accordance with the invention, one such downloaded application provides for caching information objects as described herein.
The received code may be executed by processor 1104 as it is received, and/or stored in storage device 1110, or other non-volatile storage for later execution. In this manner, computer system 1100 may obtain application code in the form of a carrier wave.
Accordingly, an object cache has been described having distinct advantages over prior approaches. In particular, this document describes an object cache that offers high performance, as measured by low latency and high throughput for object store operations, and large numbers of concurrent operations. The mechanisms described herein are applicable to a large object cache that stores terabytes of information, and billions of objects, commensurate with the growth rate.
The object cache takes advantage of memory storage space efficiency, so expensive semiconductor memory is used sparingly and effectively. The cache also offers disk storage space efficiency, so that large numbers of Internet object replicas can be stored within the finite disk capacity of the object store. The cache is alias free, so that multiple objects or object variants, with different names, but with the same content identical object content, will have the object content cached only once, shared among the different names.
The cache described herein has support for multimedia heterogeneity, efficiently supporting diverse multimedia objects of a multitude of types with size ranging over six orders of magnitude from a few hundred bytes to hundreds of megabytes. The cache has fast, usage-aware garbage collection, so less useful objects can be efficiently removed from the object store to make room for new objects. The cache features data consistency, so programmatic errors and hardware failures do not lead to corrupted data.
The cache has fast restartability, so an object cache can begin servicing requests within seconds of restart, without requiring a time-consuming database or file system check operation. The cache uses streaming I/O, so large objects can be efficiently pipelined from the object store to slow clients, without staging the entire object into memory. The cache has support for content negotiation, so proxy caches can efficiently and flexibly store variants of objects for the same URL, targeted on client browser, language, or other attribute of the client request. The cache is general purpose, so that the object store interface is sufficiently flexible to meet the needs of future media types and protocols.
The foregoing advantages and properties should be regarded as features of the technical description in this document; however, such advantages and properties do not necessarily form a part of the invention, nor are they required by any particular claim that follows this description.
In the foregoing specification, the invention has been described with reference to specific embodiments thereof and with reference to particular goals and advantages. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
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A method for consistently storing cached objects in the presence of failures is provided. This method ensures atomic object consistency--in the event of failure and restart, an object will either be completely present or completely absent from the cache, never truncated or corrupted. Furthermore, this consistency comes without any time-consuming data structure reconstruction on restart. In this scheme, objects are indexed by a directory table that is stored in main memory and mapped to non-volatile storage, and changes to the directory table are buffered into an open directory that is stored in main memory. Cache objects are either stored in volatile aggregation buffers or in segments of non-volatile disk storage called arenas. Objects are first coalesced into memory-based aggregation buffers, and later committed to disk. Locking is used to control parallel storage to aggregation buffers. Directory entries pointing to objects are only permitted to be written to persistent disk storage after the target objects are themselves committed to disk, preventing dangling pointers. Periodically, when the contents of open directory entries point to objects that are stably stored on disk, the open directory entries are copied into the directory table and committed to non-volatile storage. The disclosure also encompasses a computer program product, computer apparatus, and computer data signal configured similarly.
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FIELD OF THE INVENTION
This invention relates to linear arrays in optical scanners and methods of assembly and more particularly to a CCD array assembly permitting the economical, precision replacement of the linear array in the assembly without additional alignment.
BACKGROUND OF THE INVENTION
Conventional alignment of CCD arrays is done in a variety of ways depending on the application. In precise applications such as a photo CD scanner, an active alignment is required wherein the output of the CCD array is monitored while the location of the CCD array is adjusted. Once in the correct position, the CCD array is fixed in place. This approach produces very accurate results but is also time consuming and requires the scanner to be brought to a repair facility having very expensive fixtures for accomplishing any replacement of a failed CCD array.
SUMMARY OF THE INVENTION
The present invention provides a CCD array assembly that makes it possible to economically replace a linear array in an optical system and maintain critical alignments necessary for good image quality without requiring active alignment of the CCD array during the replacement. Accordingly, the assembly includes pre-aligned components having exactly constrained interfaces. With an exactly constrained interface, there are mounting features determined such that the X, Y, and Z positions and the three rotational positions of an object are clearly defined by these features, and only these features. Exactly constrained interfaces are also statically determinate interfaces. The components are fastenable together relative to the exactly constrained interfaces providing an aligned assembly having parts that are interchangeable. These parts can be changed without having to actively align the components.
More specifically, the CCD array is precisely located in a CCD array nest having a statically determinate interface through the use of a precision fixture which optically locates the CCD array with respect to the interface. The CCD array and the CCD array nest form a subassembly which is bonded together. The subassembly is located by the exactly constrained interface to a carrier plate and attached by screws. This carrier plate assembly is optically aligned by another precision fixture to the system optics. The CCD array and a CCD array nest subassembly can be removed and replaced in the CCD array assembly without additional alignment.
Accordingly, the CCD array assembly includes a CCD array nest having a statically determinate mounting interface bonded to the CCD array such that the CCD array is precisely aligned relative to the CCD array nest. The statically determinate interface includes two spaced nest locators and three spaced raised surfaces collectively defining a mounting plane. Apertures extend through the raised surfaces defining the mounting plane. The carrier plate has first and second sides and includes locator receivers cooperably disposed for engaging the array nest locators. The carrier plate also has threaded apertures corresponding to the apertures in the CCD array nest. It should be noted that other exactly constrained interfaces can be utilized.
A barrel frame and lens assembly is precisely aligned relative to the carrier plate assembly through the use of another precision fixture and the carrier plate is bonded to the barrel frame such that the CCD array is optically aligned for optimal performance of the CCD array. If the CCD array fails, the CCD array and CCD array nest are removable from the carrier plate via the screws which attach the subassembly to the carrier plate and a new subassembly can be installed without additional alignment.
These and other features and advantages of the invention will be more fully understood from the following detailed description of the invention taken together with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a perspective exploded view of a CCD array assembly constructed in accordance with the present invention;
FIG. 2 is a plan view of a CCD array nest;
FIG. 3 is a side elevational view of the CCD array nest of FIG. 2;
FIG. 4 is a sectional elevational view of a precision fixture illustrating the optical alignment of the CCD array in the CCD array nest;
FIG. 5 is a perspective view of a carrier plate assembly comprising the CCD array, CCD array nest, and a carrier plate; and
FIG. 6 is a side elevational view of the subassembly and carrier plate comprising the carrier plate assembly of FIG. 5 illustrating the mounting arrangement.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings in detail, numeral 10 generally indicates a CCD array assembly having a replaceable subassembly 12 comprised of a CCD array 14 and CCD array nest 16. As is hereinafter more fully described, the subassembly 12 can be replaced in the assembly 10 without additional alignment.
With reference to FIGS. 1-4, the CCD array nest 16 includes a statically determinate interface 18 defined in part by three generally concentrically disposed raised surfaces or pads 20 which define a mounting plane. The statically determinate interface 18 also includes two generally diametrically opposed array nest locators or pins 22 used to locate the CCD array nest 16 first in a fixture 24, as illustrated in FIG. 4 and subsequently in the assembly 10, as hereinafter more fully described.
With continued reference to FIG. 4, the three pads 20 locate the CCD array nest 16 in the Z direction. The two pins 22 interface with a hole 26 and slot 28 in fixture 24, locating the CCD array nest 16 in the X and Y directions and with respect to rotation around the Z axis. The CCD array nest 16 is held in place on the fixture 24 with screws 30 extending through apertures 32 in the center of each pad 20.
The CCD array 14 is optically aligned relative to the CCD array nest 16 and thereby relative to the statically determinate interface 18, by processing information received from an illuminated target 34 through a lens assembly 36 mounted on the fixture 24. The output of the CCD array 14 is processed and the information from it used to align the CCD array in all degrees of freedom for optimal performance. That alignment is achieved by holding the CCD with a fixture that has precision micrometer adjustments to move the CCD in all six degrees of freedom: X, Y, Z, rotation around X, around Y, around Z. For example, the principles used in the precision position controls that position a work piece in a machine tool can be utilized in the CCD holding fixture. Once the CCD array 14 is in a position providing optimal performance, the CCD array is bonded to the CCD array nest 16 with an adhesive. With such an alignment procedure, it becomes apparent that no precision is required of the CCD array nest 16. Therefore, part cost is reduced and performance is no longer dependent on part tolerance. Higher optimal performance is achieved in this manner.
Referring again to FIG. 1, and with reference to FIGS. 5 and 6, the CCD array assembly 10 includes a carrier plate 38 having first and second sides 40, 42 respectively. The first side 40 engages the statically determinate interface 18 of the replaceable subassembly 12 and includes locator receivers defined by a hole 26' and slot 28' cooperably disposed for engaging pins 22. The first side 40 thereby provides a corresponding interface for receiving the array nest 16 as that of fixture 24. Screws 30' are used to attach the subassembly 12 to the carrier plate 38 forming a carrier plate assembly 39.
The carrier plate 38 with the attached subassembly 12 is bonded by the second side 42 to a barrel frame and lens assembly 44 after alignment as hereinbelow described to complete the CCD array assembly 10. The barrel frame and lens assembly 44 includes a barrel frame 46 and a lens 48 aligned by precision fixturing, not shown. The alignment of the barrel frame 46 and lens 48 can be preserved at this point in the process by bonding together with an adhesive. Alternatively, the alignment can be fixed after several more steps. By fixing the barrel frame 46 and lens 48 in connection with alignment of the carrier plate 38 and subassembly 12, the flexibility of adjusting the magnification of the optical system is achieved. This alignment is accomplished in an iterative manner.
In like manner, as the hereinabove described optical alignment procedure preceding the bonding of the CCD array 14 and array nest 16, the subassembly 12 and the carrier plate 38 are mounted in another fixture, not shown, and the barrel frame and lens assembly 44 is secured in yet another fixture, not shown, that has an illuminated target.
The subassembly 12 and carrier plate 38 are moved in a precise manner relative to the barrel frame and lens assembly 44 to achieve proper alignment. The output of the CCD array 14 is processed and the information from it used to align the carrier plate and CCD array subassembly 12 in all degrees of freedom for optimal performance. Once the subassembly 12 and carrier plate 38 are in a position of optimal performance of the CCD array 14, the second side 42 of the carrier plate 38 is bonded to the barrel frame and lens assembly 44 by an adhesive.
If the barrel frame 46 has not been previously bonded to adjust for magnification, it could be bonded at this point. If the magnification does not meet the requirements, the lens 48 can be moved axially to change the magnification and the alignment process repeated. This would be an iterative process that may have to be repeated until the magnification meets the requirements of the scanner.
If the CCD array 14 fails in use, the subassembly 12 consisting of the CCD array 14 and array nest 16 is removable from the carrier plate 38 by unfastening screws 30' and removing the subassembly 12 from the carrier plate assembly 39. A new subassembly 12 is replaceable on the carrier plate 38, and without any active optical alignment, the alignment of the subassembly 12 is maintained through the statically determinate interface 18 engagement with the carrier plate.
The terms "optical alignment", "optically aligned" and "optically located" as used herein and in the following claims refer to the previously described methods of alignment of the CCD array 14 with the nest 16 and the carrier plate assembly 39 with the barrel frame and lens assembly 44 by positioning the CCD array 14 or carrier plate assembly 39 for optimal performance of the CCD array by processing information received from an illuminated target through a lens in a fixture or in the barrel frame and lens assembly.
Although the invention has been described by reference to a specific embodiment, it should be understood that numerous changes may be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the described embodiment, but that it have the full scope defined by the language of the following claims.
Parts List
10. CCD array assembly
12. subassembly
14. CCD array
16. CCD array nest
18. interface
20. pads
22. pins
24. fixture
26. hole
26'. hole
28. slot
28'. slot
30. screws
30'. screws
32. apertures
34. target
36. fixture lens assembly
38. carrier plate
39. carrier plate assembly
40. first side
42. second side
44. assembly
46. barrel frame
48. lens
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A CCD array assembly for use in a scanner, includes a CCD array optically aligned relative to a CCD array nest and affixed thereto to form a replaceable subassembly. The CCD array nest has an outwardly facing statically determinate or exactly constrained interface mounting surface. A carrier plate with the CCD array assembly removably attached thereto is optically aligned and affixed to a barrel frame and lens assembly. The subassembly is removably attachable to the carrier plate allowing replacement of a failed CCD array without additional alignment.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of U.S. Provisional Patent Application Ser. No. 60/592,708, filed on Jul. 30, 2004, which application is herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to methods and apparatus for drilling with top drive systems. Particularly, the invention relates to methods and apparatus for retrieving a downhole tool through a top drive system. More particularly still, the invention relates to running a wireline through the top drive system to retrieve the downhole tool and running a wireline access below the top drive system. The invention also relates to performing a cementing operation with the top drive system.
2. Description of the Related Art
One conventional method to complete a well includes drilling to a first designated depth with a drill bit on a drill string. Then, the drill string is removed, and a first string of casing is run into the wellbore and set in the drilled out portion of the wellbore. Cement is circulated into the annulus behind the casing string and allowed to cure. Next, the well is drilled to a second designated depth, and a second string of casing, or liner, is run into the drilled out portion of the wellbore. The second string is set at a depth such that the upper portion of the second string of casing overlaps the lower portion of the first string of casing. The second string is then fixed, or “hung” off of the existing casing by the use of slips which utilize slip members and cones to wedgingly fix the second string of casing in the wellbore. The second casing string is then cemented. This process is typically repeated with additional casing strings until the well has been drilled to a desired depth. Therefore, two run-ins into the wellbore are required per casing string to set the casing into the wellbore.
As more casing strings are set in the wellbore, the casing strings become progressively smaller in diameter in order to fit within the previous casing string. In a drilling operation, the drill bit for drilling to the next predetermined depth must thus become progressively smaller as the diameter of each casing string decreases in order to fit within the previous casing string. Therefore, multiple drill bits of different sizes are ordinarily necessary for drilling in well completion operations.
Another method of performing well completion operations involves drilling with casing, as opposed to the first method of drilling and then setting the casing. In this method, the casing string is run into the wellbore along with a drill bit for drilling the subsequent, smaller diameter hole located in the interior of the existing casing string. The drill bit is operated by rotation of the drill string from the surface of the wellbore, and/or rotation of a downhole motor. Once the borehole is formed, the attached casing string may be cemented in the borehole. The drill bit is either removed or destroyed by the drilling of a subsequent borehole. The subsequent borehole may be drilled by a second working string comprising a second drill bit disposed at the end of a second casing that is of sufficient size to line the wall of the borehole formed. The second drill bit should be smaller than the first drill bit so that it fits within the existing casing string. In this respect, this method typically requires only one run into the wellbore per casing string that is set into the wellbore.
In some operations, the drill shoe disposed at the lower end of the casing is designed to be drilled through by the subsequent casing string. However, retrievable drill bits and drilling assemblies have been developed to reduce the cost of the drilling operation. These drilling assemblies are equipped with a latch that is operable to selectively attach the drilling assembly to the casing. In this respect, the drilling assembly may be preserved for subsequent drilling operations.
It is known in the industry to use top drive systems to rotate the casing string and the drill shoe to form a borehole. Top drive systems are equipped with a motor to provide torque for rotating the drilling string. Most existing top drives use a threaded crossover adapter to connect to the casing. This is because the quill of the top drive is not sized to connect with the threads of the casing.
More recently, top drive adapters has been developed to facilitate the casing running process. Top drive adapters that grip the external portion of the casing are generally known as torque heads, while adapters that grip the internal portion of the casing are generally known as spears. An exemplary torque head is disclosed in U.S. patent application Ser. No. 10/850,347, entitled Casing Running Head, which application was filed on May 20, 2004 by the same inventor of the present application. An exemplary spear is disclosed in U.S. Patent Application Publication No. 2005/0051343, by Pietras, et al. These applications are assigned to the assignee of the present application and are herein incorporated by reference in their entirety.
One of the challenges of drilling with casing is the retrieval of the drilling assembly. For example, the drilling operation may be temporarily stopped to repair or replace the drilling assembly. In such instances, a wireline may be used to retrieve the latch and the drilling assembly. However, many existing top drives are not equipped with an access for the insertion or removal of the wireline, thereby making the run-in of the wireline more difficult and time consuming. Additionally, during the temporary stoppage to retrieve the drilling assembly, fluid circulation and casing movement is also typically stopped. As a result, the casing in the wellbore may become stuck, thereby hindering the rotation and advancement of the casing upon restart of the drilling operation.
There is a need, therefore, for methods and apparatus for retrieving the drilling assembly during and after drilling operations. There is also a need for apparatus and method for fluid circulation during the drilling assembly retrieval process. There is a further need for apparatus and methods for running a wireline while drilling with casing using a top drive. There is yet a further need for methods and apparatus for accessing the interior of a casing string connected to a top drive.
SUMMARY OF THE INVENTION
In one embodiment, a top drive system for forming a wellbore is provided with an access tool to retrieve a downhole tool. The top drive system for drilling with casing comprises a top drive; a top drive adapter for gripping the casing, the top drive adapter operatively connected to the top drive; and an access tool operatively connected to the top drive and adapted for accessing a fluid passage of the top drive system. In one embodiment, the top drive system is used for drilling with casing operations.
In another embodiment, a method for retrieving a downhole tool through a tubular coupled to a top drive adapter of a top drive system is provided. The method comprises coupling an access tool to the top drive system, the access tool adapted to provide access to a fluid path in the top drive system and inserting a conveying member into the fluid path through the access tool. The method also includes coupling the conveying member to the downhole tool and retrieving the downhole tool. In another embodiment, the method further comprises reciprocating the tubular. In yet another embodiment, the method further comprises circulating fluid to the tubular. Preferably, the tubular comprises a casing.
In another embodiment still, a method for releasing an actuating device during drilling using a top drive system is provided. The method comprises providing the top drive system with a top drive, a top drive adapter, and a launching tool, the launching tool retaining the actuating device, and operatively coupling the top drive, the top drive adapter, and the launching tool. The method also includes gripping a tubular using the top drive adapter and actuating the launching tool to release the actuating device.
In another embodiment still, a method for performing a cementing operation using a top drive system is provided. The method comprises providing the top drive system with a top drive, a top drive adapter, and a cementing tool and operatively coupling the top drive, the top drive adapter, and the cementing tool. The method also comprises gripping the casing using the top drive adapter and supplying a cementing fluid through the cementing tool.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features and other features contemplated and claimed herein are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
FIG. 1 shows an exemplary embodiment of a top drive system having an access tool.
FIG. 2 shows an alternative top drive system having another embodiment of an access tool.
FIG. 3 shows another embodiment of an access tool.
FIG. 4 shows yet another embodiment of an access tool.
FIG. 5 shows an alternative top drive system equipped with yet another embodiment of an access tool.
FIG. 6 shows yet another embodiment of an access tool.
FIG. 6A is a partial cross-sectional view of the access tool of FIG. 6 .
FIG. 7 is a partial cross-sectional view of another embodiment of an access tool.
FIG. 8 shows an embodiment of an access tool having a launching tool.
FIG. 8A is a cross-sectional view of the access tool of FIG. 8 .
FIG. 8B illustrates an embodiment of retaining a plug in a casing string.
FIG. 8C illustrates another embodiment of retaining a plug in a casing string.
FIG. 9 shows an alternative top drive system having a cementing tool.
FIG. 10 is a partial cross-sectional view of the cementing tool of FIG. 9 .
FIG. 10A is another cross-sectional view of the cementing tool of FIG. 9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In one embodiment, a top drive system for drilling includes a top drive adapter for gripping and rotating the casing and a top drive access tool. The top drive access tool is adapted to allow access into the various components connected to the top drive. The access tool is equipped with a sealing member to prevent leakage and hold pressure during fluid circulation. In another embodiment, the access tool is adapted to allow the top drive to reciprocate the casing during wireline work.
FIG. 1 shows an embodiment of a top drive system 100 fitted with a top drive access tool 110 . As shown, the system 100 includes a spear type top drive adapter 20 and a top drive 10 for energizing the spear 20 . The spear 20 includes radially actuatable gripping members 22 for engaging the inner diameter of the casing. Although a mechanically actuated spear is preferred, spears actuated using hydraulics, pneumatics, or electric are equally suitable. The lower portion of the spear 20 includes a valve 24 for supplying fluid and a seal member 26 to prevent leakage. Fluids such as drilling mud may be introduced into the top drive system 100 through a fluid supply line 5 disposed at an upper portion of the top drive 10 . An elevator 30 is suspended below the top drive 10 by a pair of bails 35 coupled to the top drive 10 . It must be noted that in addition to the spear, other types of top drive adapters such as a torque head are also contemplated.
In one embodiment, the top drive access tool 110 is coupled to the upper portion of the top drive 10 . The access tool 110 is adapted to allow wireline access into the interior of the casing in order to perform wireline operations such as retrieval of the drilling assembly or the latch attached to a drilling assembly. As shown in FIG. 1 , the access tool 110 includes a connection member 112 for connecting to the top drive 10 . The connection member 112 includes a bore to receive the wireline 15 and a pack-off assembly 114 for preventing leakage. The pack-off assembly 114 may comprise an elastomeric seal element and sized to accommodate different wireline sizes. A sheave assembly 116 is connected to the connection member 112 . The sheave assembly 116 facilitates and supports the wireline 15 for entry into the top drive 10 . Preferably, the sheave assembly 116 is arranged such that it does not obstruct the operation of the traveling block, which is typically used to translate the top drive 10 . In one embodiment, the sheave assembly 116 includes two wheels 117 A, 117 B adapted for operation with the top drive 10 . The wheels 117 A, 117 B may include grooves disposed around the circumference of the wheels 117 A, 117 B for receiving the wireline 15 . The wireline 15 may be routed around the wheels 117 A, 117 B of the sheave assembly 116 to avoid the traveling block and directed into the pack-off assembly 114 and the connection member 112 . In another embodiment, the fluid supply line 5 may be connected to the connection member 112 of the access tool 110 . A suitable access tool is disclosed in U.S. Pat. No. 5,735,351 issued to Helms, which patent is herein incorporated by reference in its entirety. During wireline operations, the top drive system 100 provided in FIG. 1 may be operated to reciprocate the casing in the wellbore and circulate fluid through the casing. It is believed that these operations will reduce the likelihood of the casing sticking to the wellbore. In addition to a wireline 15 , the embodiments described herein are equally applicable to a cable or other types of conveying members known to a person of ordinary skill in the art.
FIG. 2 illustrates another embodiment of a top drive system 200 equipped with an access tool 210 . Similar to the embodiment shown in FIG. 1 , the top drive system 200 includes a spear type top drive adapter 20 coupled to the top drive 10 . However, the elevator and the bails have been removed for clarity. In this embodiment, the access tool 210 is disposed between the top drive 10 and the spear 20 . The access tool 210 defines a tubular having a main portion 212 and one or more side portions 214 attached thereto. The upper end of the main portion 212 is connected to the top drive 10 , and the lower end is connected to the spear 20 . Extension subs or tubulars 220 A, 220 B may be used to couple the access tool 210 to the top drive 10 or the spear 20 . A central passage 213 in the main portion 212 is adapted for fluid communication with the top drive 10 and the spear 20 . The side entry portions 214 have side entry passages 215 in fluid communication with the central passage 213 . In the embodiment shown, the access tool 210 includes two side portions 214 . Each side portion 214 may include a pack-off assembly 230 to prevent leakage and hold pressure. In this respect, the pack-off assembly 230 also functions as a blow out preventer. In operation, the wireline 15 accesses the casing through one of the side portions 214 . Additionally, the access tool 210 allows the top drive system 200 to reciprocate the casing and circulate drilling fluid using the spear 20 during wireline operation. Fluid may be supplied to the top drive 10 through the fluid supply line 5 . In another embodiment, the access tool 210 may optionally include a valve 216 to isolate the fluid in the top drive 10 from fluid supplied through one of the side entry passages 215 . Exemplary valves include a ball valve, one-way valves, or any suitable valve known to a person of ordinary skill in the art.
In another embodiment, the top drive system 240 may include a sheave assembly 250 attached to the pack-off assembly 245 , as illustrated in FIG. 3 . The sheave assembly 250 may include a sheave wheel 255 to reduce the friction experienced by the wireline 15 . In yet another embodiment, the top drive system 240 may include two spears 261 , 262 , two torque heads, or combinations thereof to increase the speed of modifying the top drive 10 for wireline operation. As shown, a first spear 261 is connected to the top drive 10 and initially retains a casing string for drilling operations. When wireline operation is desired, the first spear 261 may release the casing and retain an access assembly 270 having an access tool 275 , an extension tubular 277 , and a spear 262 . The spear 262 of the access assembly 270 can now be used to retain the casing string and reciprocate the casing string and/or circulate fluid during the wireline operation. After completion of the wireline operation, the access assembly 270 may be quickly removed by disengagement of the spears 261 , 262 . It should be appreciated the spears may be torque heads or a combination of spears and torque heads.
FIG. 4 is a partial cross-sectional view of another embodiment of the access system 230 . The access system 230 is attached to a spear 20 having gripping members 22 adapted to retain a casing. The access system 230 includes a main portion 231 and a side portion 233 . It can be seen that the side entry passage 234 is in fluid communication with the main passage 232 . The side portion 233 is equipped with a pack-off assembly 235 and a sheave assembly 236 . The sheave assembly 236 includes a sheave wheel 237 supported on a support arm 238 that is attached to the main portion 231 . As shown, a cable 15 has been inserted through the pack-off assembly 235 , the side entry passage 234 , the main passage 232 , and the spear 20 .
In yet another embodiment, a top drive system 280 may include an external gripping top drive adapter 285 for use with the top drive 10 and the access tool 290 , as illustrated in FIG. 5 . An exemplary top drive adapter is disclosed in U.S. patent application Ser. No. 10/850,347, entitled Casing Running Head, filed on May 20, 2004 by Bernd-Georg Pietras. The application is assigned to the same assignee as the present application and is herein incorporated by reference in its entirety. In this embodiment, the top drive adapter 285 , also known as a torque head, may release the casing and retain the access tool 290 . The access tool 290 , as shown, is adapted with one side entry portion 292 having a pack-off assembly 293 and a sheave assembly 294 . A casing collar clamp 295 attached to the access tool 290 is used to retain the casing string 3 . It must be noted that other types of casing retaining devices such as an elevator or a cross-over adapter may be used instead of the casing collar clamp, as is known to a person of ordinary skill in the art.
FIG. 6 illustrates another embodiment of the access system 300 . The access system 300 includes an upper manifold 311 and a lower manifold 312 connected by one or more flow subs 315 . Each manifold 311 , 312 includes a connection sub 313 , 314 for coupling to the top drive 10 or the spear 20 . FIG. 6A is a cross-section view of the access system 300 . Fluid flowing through the upper connection sub 313 is directed toward a manifold chamber 317 in the upper manifold 311 , where it is then separated into the four flow subs 315 . Fluid in the flow subs 315 aggregates in a chamber 318 of the lower manifold 312 and exits through the lower connection sub 314 , which channels the fluid to the spear 20 . Although the embodiment is described with four flow subs, it is contemplated any number of flow subs may be used.
The lower manifold 312 includes an access opening 320 for insertion of the wireline 15 . As shown, the opening 320 is fitted with a pack-off assembly 325 to prevent leakage and hold pressure. Preferably, the opening 320 is in axial alignment with the spear 20 and the casing 3 . In this respect, the wireline 15 is centered over the hoisting load, thereby minimizing wireline wear, as shown in FIG. 6 . The access system 300 may also include a sheave assembly 330 to facilitate the axial alignment of the wireline 15 with the opening 320 . The sheave wheel 331 is positioned with respect to the upper manifold 311 such that the wireline 15 routed therethrough is substantially centered with the opening 320 .
In another embodiment, a swivel may be disposed between the access system 300 and the spear 20 . An exemplary swivel may comprise a bearing system. The addition of the swivel allows the casing string 3 to be rotated while the sheave assembly 330 remains stationary. The casing string 3 may be rotated using a kelly, a rotary table, or any suitable manner known to a person of ordinary skill in the art.
FIG. 7 illustrates another embodiment of an access tool 335 . The access tool 335 includes a housing 337 having an upper connection sub 338 and a lower connection sub 339 . The connection subs 338 , 339 are adapted for fluid communication with a chamber 336 in the housing 337 . The housing 337 includes an access port 340 for receiving the wireline 15 . The access port 340 is equipped with a pack-off assembly 341 to prevent fluid leakage and hold pressure. In one embodiment, a sheave assembly 345 is installed in the chamber 336 to facilitate movement of the wireline 15 . Preferably, the sheave assembly 345 is positioned such that the wireline 15 is aligned with the lower connection sub 339 . In another embodiment, a fluid diverter 342 may be installed at the upper portion of the chamber 336 to divert the fluid entering the chamber 336 from the upper connection sub 338 . The fluid diverter 342 may be adapted to diffuse the fluid flow, redirect the fluid flow, or combinations thereof.
In another embodiment, the top drive system 350 may be equipped with a tool 360 for releasing downhole actuating devices such as a ball or dart. In one embodiment, the launching or releasing tool 360 may be used to selectively actuate or release a plug 371 , 372 during a cementing operation, as shown in FIGS. 8-8A . FIG. 8A is a cross-sectional view of the access tool 350 with the launching tool 360 . The access tool 350 is similar to the access tool 300 of FIG. 6 . As shown, the access tool 350 includes an upper manifold 377 and a lower manifold 376 connected by one or more flow subs 375 . Each manifold 377 , 376 includes a connection sub 373 , 374 for coupling to the top drive 10 or the spear 20 . In FIG. 8A , the launching tool 360 has replaced the packing-off assembly 325 shown in FIG. 6 . The launching tool 360 is adapted to selectively drop the two balls 361 , 362 downhole, thereby causing the release of the two plugs 371 , 372 attached to a lower portion of the spear 20 . The launching tool 360 includes a bore 363 in substantial alignment with the bore of the connection sub 374 . The balls 361 , 362 are separately retained in the bore by a respective releasing pin 367 , 368 . Fluids, such as cement, may be pumped through upper portion 364 of the launching tool 360 and selectively around the balls 361 , 362 . Actuation of the releasing pin 367 , 368 will cause these balls 361 , 362 , aided by the fluid pumped behind, to be launched into the flow stream to release the plugs 371 , 372 . It must be noted that any suitable launching tool known to a person of ordinary skill in the art may also be adapted for use with the access tool. In addition, the components may be arranged in any suitable manner. For example, the launching tool 360 may be disposed between the access tool 350 and the spear 20 . In this respect, fluid exiting the access tool 350 will flow through the launching tool 360 before entering the spear 20 .
In operation, the first release pin 367 is deactivated to allow the first ball 361 to drop into the lower manifold 376 and travel downward to the spear 20 . The first ball 361 is preferably positioned between the drilling fluid and the cement. The first ball 361 will land and seat in the first, or lower, plug 371 and block off fluid flow downhole. Fluid pressure build up will cause the first plug 371 to release downhole. As it travels downward, the first plug 371 functions as a buffer between the drilling fluid, which is ahead of the first plug 371 , and the cement, which is behind the first plug 371 . When sufficient cement has been introduced, the second release pin 368 is deactivated to drop the second ball 362 from the launching tool 360 . The second ball 362 will travel through the bore and land in the second, or upper, plug 372 . Seating of the ball 362 will block off fluid flow and cause an increase in fluid pressure. When a predetermined fluid pressure is reached, the second plug 372 will be released downhole. The second plug 372 will separate the cement, which is in front of the second plug 372 , from the drilling fluid or spacer fluid, which is behind the second plug 372 .
In another embodiment, the plugs may be coupled to the casing string instead of the top drive adapter. As shown in FIG. 8C , a plug 400 is provided with a retaining member 410 for selective attachment to a casing string 3 . Preferably, the retaining member 410 attaches to the casing string 3 at a location where two casing sections 403 , 404 are threadedly connected to a coupling 405 . Particularly, the retaining member 410 includes a key 412 that is disposable between the ends of the two casing sections 403 , 404 . The plug 400 , in turn, is attached to the retaining member 410 using a shearable member 420 . The plug 400 and the retaining member 410 include a bore 422 for fluid flow therethrough. The plug 400 also includes a seat 425 for receiving an actuatable device such as a ball or dart. Preferably, the retaining member 410 and the plug 400 are made of a drillable material, as is known to a person of ordinary skill in the art. It must be noted that although only one plug is shown, more than one plug may be attached to the retaining member for multiple plug releases.
In operation, a ball dropped from the launching tool 360 will travel in the wellbore until it lands in the seat 425 of the plug 400 , thereby closing off fluid flow downhole. Thereafter, increase in pressure behind the ball will cause the shearable member 420 to fail, thereby releasing the plug 400 from the retaining member 410 . In this manner, a plug 400 may be released from various locations in the wellbore.
FIG. 8B shows another embodiment of coupling the plug to the casing string. In this embodiment, the retaining member comprises a packer 440 . The packer 440 may comprise a drillable packer, a retrievable packer, or combinations thereof. The packer 440 includes one or more engagement members 445 for gripping the wall of the casing 3 . An exemplary packer is disclosed in U.S. Pat. No. 5,787,979, which patent is herein incorporated by reference in its entirety. As shown, two plugs 451 , 452 are selectively attached to the packer 440 and are adapted for release by an actuatable device such as a ball. Preferably, the first, or lower, plug 451 has a ball seat 453 that is smaller than the ball seat 454 of the second, or upper, plug 452 . In this respect, a smaller ball launched from the launching tool may bypass the second plug 452 and land in the seat 453 of the first plug 451 , thereby releasing the first plug 451 . Thereafter, the second plug 452 may be released by a larger second ball. In this manner, the plugs 451 , 452 may be selectively released from the packer 440 . After the plugs 451 , 452 have been released, the packer 440 may be retrieved or drilled through.
In another embodiment, the launching tool may be installed on an access tool similar to the one shown in FIG. 3 . For example, the sheave assembly 236 and pack-off 235 may be removed and a launching tool such as a ball launcher with a top entry may be installed on a side portion 233 . In this respect, one or more balls may be launched to release one or more cementing plugs located below the spear or torque head.
In another aspect, the top drive system 500 may include a top drive 510 , a cementing tool 515 , and a top drive adapter, as illustrated in FIG. 9 . As shown, the top drive adapter comprises a spear 520 . The cementing tool 515 is adapted to selectively block off fluid flow from the top drive 510 during cementing operations.
FIG. 10 is a partial cross-sectional view of an embodiment of the cementing tool 515 . The cementing tool 515 includes a central bore 522 for fluid communication with the top drive 510 and the spear 520 . A valve 525 is disposed in an upper portion of the bore 522 to selectively block off fluid communication with the top drive 510 . The valve 525 is actuated between an open position and a close position by operation of a piston 530 . As shown, the piston 530 is biased by a biasing member 532 to maintain the valve 525 in the open position. To close the valve 525 , an actuating fluid is introduced through a fluid port 541 to move the piston 530 toward the valve 525 . In this respect, movement of the piston 530 compresses the biasing member 532 and closes the valve 525 , thereby blocking off fluid communication of the cementing tool 515 and the top drive 510 . Thereafter, cement may be introduced into the bore 522 through the cementing port 545 .
In another aspect, the cementing tool 515 may be adapted to release one or more actuating devices into the wellbore. In the embodiment shown in FIG. 10 , the cementing tool 515 is adapted to selectively launch three balls 561 . It must be noted that the cementing tool 515 may be adapted to launch any suitable number or type of actuating devices. Each ball 561 is retained by a release piston 550 A before being dropped into the wellbore. The piston 550 A is disposed in an axial channel 555 formed adjacent to the bore 522 . In one embodiment, the piston 550 A has a base 551 attached to the body of the cementing tool 515 and a piston head 552 that is extendable or retractable relative to the base 551 . The outer diameter of a portion of the piston head 552 is sized such that an annulus 553 is formed between the piston head 552 and the wall of the axial channel 555 . Seal members or o-rings may be suitably disposed in the base 551 and the piston head 552 to enclose the annulus 553 . The annulus 553 formed is in selective fluid communication with an actuating fluid port 542 A. In this respect, the actuating fluid may be supplied into the annulus 553 to extend the piston head 552 relative to the base 551 , or relieved to retract the piston head 552 . Preferably, the piston head 552 is maintained in the retracted position by a biasing member 557 , as shown FIG. 10 .
The release piston 550 A is provided with an opening 563 to house the ball 561 and a cement bypass 565 . In the retracted position shown, the cement bypass 565 is in fluid communication with a radial fluid channel 570 A connecting the cement port 545 to the bore 522 . In this respect, cementing fluid may be supplied into the bore 522 without causing the ball 561 to release. When the piston head 552 is extended, the opening 563 is, in turn, placed in fluid communication with the radial fluid channel 570 A.
As discussed, the cementing tool 515 may be adapted to release one or more actuating devices. In the cross-sectional view of FIG. 10A , it can be seen that three release pistons 550 A, 550 B, 550 C are circumferentially disposed around the bore 522 . Cementing fluid coming in from either of the cementing ports 545 , 545 A is initially circulated in an annular channel 575 . Three radial fluid channels 570 A, 570 B, 570 C connect the annular channel 575 to the bore 522 of the cementing tool 515 . Each radial fluid channel 570 A, 570 B, 570 C also intersect the cement bypass 565 of a respective release piston 550 A, 550 B, 550 C.
To release the first ball 561 , actuating fluid is introduced through the fluid port 542 A and into the annulus 553 of the first release piston 550 A. In turn, the piston head 552 is extended to place the opening 563 in fluid communication with the radial fluid channel 570 A. Thereafter, cement flowing through the cementing port 545 , the annular channel 575 , and the radial channel 570 A urges to the ball 561 toward the bore 522 , thereby dropping the ball 561 downhole. Because either position of the piston head 552 provides for fluid communication with the cementing port 545 , the piston head 552 may remain in the extended position after the first ball 561 is released.
To release the second ball, actuating fluid is introduced through the second fluid port 542 B and into the annulus 553 of the second release piston 550 B. In turn, the piston head 552 is extended to place the opening 563 in fluid communication with the radial fluid channel 570 B. Thereafter, cement flowing through the radial channel 570 B urges to the ball 561 toward the bore 522 , thereby dropping the ball 561 downhole. The third ball may be released in a similar manner by supplying actuating fluid through the third fluid port 542 C.
In another aspect, the cementing tool 515 may optionally include a swivel mechanism to facilitate the cementing operation. In one embodiment, the fluid ports 541 , 542 A, 542 B, 542 C and the cementing port 545 may be disposed on a sleeve 559 . The sleeve 559 may be coupled to the body of the cementing tool using one or more bearings 558 A, 558 B. As shown in FIG. 10 , two sets of bearings 558 A, 558 B are disposed between the sleeve 559 and the body of the cementing tool 515 . In this respect, the body of the cementing tool 515 may be rotated by the top drive 10 without rotating the ports 541 , 542 A, 542 B, 542 C, 545 and the fluid lines connected thereto. During the cementing operation, the swivel mechanism of the cementing tool 515 allows the top drive 10 to rotate the drill string 3 , thereby providing a more efficient distribution of cementing in the wellbore.
In another embodiment, the cementing tool 515 may include additional fluid ports to introduce fluid into the top drive system. For example, hydraulic fluids may be supplied through the additional fluid ports to operate the spear, torque head, weight/thread compensation sub, or other devices connected to the top drive. Additionally, operating fluids may also be supplied through one of the existing ports 541 , 542 A, 542 B, 542 C, 545 of the cementing tool 515 .
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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In one embodiment, a top drive system for drilling with casing is provided with an access tool to retrieve a downhole tool. The top drive system for drilling with casing comprises a top drive; a top drive adapter for gripping the casing, the top drive adapter operatively coupled to the top drive; and an access tool coupled to the top drive and adapted for accessing a fluid passage of the top drive system. In another embodiment, a method for retrieving a downhole tool through a tubular coupled to a top drive adapter of a top drive system is provided. The method comprises coupling an access tool to the top drive system, the access tool adapted to provide access to a fluid path in the top drive system and inserting a conveying member into the fluid path through the access tool.
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BACKGROUND OF THE INVENTION
This invention is generally directed to titanyl phthalocyanines and processes for the preparation thereof, and more specifically the present invention is directed to processes for obtaining titanyl phthalocyanine polymorphs or crystal forms, including Type X, and layered photoconductive members comprised of the aforementioned titanyl phthalocyanine polymorphs. In one embodiment, the present invention is directed to a process for the preparation of stable Type X titanyl phthalocyanine by the treatment thereof with an organic solvent, such as fluorobenzene. In one embodiment, the process of the present invention comprises the treatment or washing of Type X titanyl phthalocyanine, the preparation of which is disclosed, for example, in the copending patent applications mentioned herein, with fluorobenzene, thereby providing a stable Type X that does not reconvert to Type IV, or Type II titanyl phthalocyanine, and wherein an imaging member with the Type X possesses improved photosensitivity. In an embodiment, the process of the present invention comprises the reaction of titanium tetra(alkoxide) with diiminoisoindolene in a solvent such as chloronaphthalene; dissolving the resulting pigment in a solvent mixture of trifluoroacetic acid and methylene chloride; and thereafter precipitating the desired titanyl phthalocyanine polymorph by, for example, adding with stirring the aforementioned mixture to a mixture of methanol and water, separating the product therefrom by, for example, filtration, and washing the product obtained with fluorobenzene. The titanyl phthalocyanines, especially the X form, can be selected as an organic photogenerator pigment in photoresponsive imaging members containing charge, especially hole transport layers such as aryl amine hole transport molecules. The aforementioned photoresponsive imaging members can be negatively charged when the photogenerating layer is situated between the hole transport layer and the substrate, or positively charged when the hole transport layer is situated between the photogenerating layer and the supporting substrate. The layered photoconductor imaging members can be selected for a number of different known imaging and printing processes including, for example, electrophotographic imaging processes, especially xerographic imaging and printing processes wherein negatively charged or positively charged images are rendered visible with toner compositions of the appropriate charge. Generally, the imaging members are sensitive in the wavelength regions of from about 700 to about 850 nanometers, thus diode lasers can be selected as the light source.
Certain titanium phthalocyanine pigments have been known, reference for example the publication WW 2(PB 85172 Fiat Final Report 1313, Feb. 1, 1948). However, unlike other phthalocyanines such as metal-free, copper, iron and zinc phthalocyanines, titanium phthalocyanines have had minimum commercial use. Titanyl phthalocyanines or oxytitanium phthalocyanines are known to absorb near-infrared light around 800 nanometers and a number of such pigments have been illustrated in the prior art as materials for IR laser optical recording material, reference for example BASF German 3,643,770 and U.S. Pat. No. 4,458,004. The use of certain titanium phthalocyanine pigments as a photoconductive material for electrophotographic applications is known, reference for example British Patent Publication 1,152,655, the disclosure of which is totally incorporated herein by reference. Also, U.S. Pat. No. 3,825,422 illustrates the use of titanyl phthalocyanine as a photoconductive pigment in an electrophotographic process known as particle electrophoresis. Additionally, the utilization of certain titanyl phthalocyanines and substituted derivatives thereof in a dual layer electrographic device is illustrated in EPO 180931, May 14, 1986. Moreover, the use of tetra- and hexadeca-fluoro-substituted titanyl phthalocyanine in an electrophotographic device is illustrated in U.S. Pat. No. 4,701,396. In Japanese Patent Publication 64-171771, August, 1986, there is illustrated the use of titanyl phthalocyanine, which has been treated with a hot solvent, in electrophotography. Further, in German 3,821,628 there is illustrated the utilization of certain titanyl phthalocyanines, and other pigments in electrophotography, and wherein the titanyl phthalocyanines have been purified primarily to reduce the level of ash, volatile contaminants and sodium to below specified levels.
In Japanese 62-256865 there is disclosed, for example, a process for the preparation of pure Type I involving the addition of titanium tetrachloride to a solution of phthalonitrile in an organic solvent which has been heated in advance to a temperature of from 160° to 300° C. In Japanese 62-256866, there is illustrated, for example, a method of preparing the aforementioned polymorph which involves the rapid heating of a mixture of phthalonitrile and titanium tetrachloride in an organic solvent at a temperature of from 100° to 170° C. over a time period which does not exceed one hour. In Japanese 62-256867, there is described, for example, a process for the preparation of pure Type II (B) titanyl phthalocyanine, which involves a similar method to the latter except that the time to heat the mixture at from 100° to 170° C., is maintained for at least two and one half hours. Types I and II, in the pure form obtained by the process of the above publications, apparently afforded layered photoresponsive imaging members with excellent electrophotographic characteristics.
In Mita EPO Patent Publication 314,100, there is illustrated the synthesis of TiOPc by, for example, the reaction of titanium alkoxides and diiminoisoindolene in quinoline or an alkylbenzene, and the subsequent conversion thereof to an alpha Type pigment (Type II) by an acid pasting process, whereby the synthesized pigment is dissolved in concentrated sulfuric acid, and the resultant solution is poured onto ice to precipitate the alpha-form, which is filtered and washed with methylene chloride. This pigment, which was blended with varying amounts of metal free phthalocyanine, could be selected as the electric charge generating layer in layered photoresponsive imaging members with a high photosensivity at, for example, 780 nanometers.
In the aforementioned documents, certain synthesis and processing conditions are disclosed for the preparation of the titanyl phthalocyanine pigments. As mentioned in the textbook Phthalocyanine Compounds by Moser and Thomas, the disclosure of which is totally incorporated herein by reference, polymorphism or the ability to form distinct solid state forms is well known in phthalocyanines. For example, metal-free phthalocyanine is known to exist in at least 5 forms designated as alpha, beta, pi, X and tau. Copper phthalocyanine crystal forms known as alpha, beta, gamma, delta, epsilon and pi are also described. These different polymorphic forms are usually distinguishable on the basis of differences in the solid state properties of the materials which can be determined by measurements, such as Differential Scanning Calorimetry, Infrared Spectroscopy, Ultraviolet-Visible-Near Infrared spectroscopy and, especially, X-Ray Powder Diffraction techniques. There appears to be general agreement on the nomenclature used to designate specific polymorphs of commonly used pigments such as metal-free and copper phthalocyanine. However, this does not appear to be the situation with titanyl phthalocyanines as different nomenclature is selected in a number of instances. For example, reference is made to alpha, beta, A,B, C, y, and m forms of TiOPc (titanyl phthalocyanine) with different names being used for the same form in some situation. It is believed that five main crystal forms of TiOPc are known, that is Types X, I, II, III, and IV. X-ray powder diffraction traces (XRPDs) obtained from these 5 forms are shown in FIGS. 1A, 1B, 1C, 1D, and 1E. Subclasses of these forms with broad, more poorly resolved peaks than those shown in FIGS. 1A, 1B, 1C and 1D can be envisioned, however, the basic features of the diffractograms indicate the major peaks in the same position although the smaller peaks can be unresolved. This broadening of XRPD peaks is generally found in pigments having a very small particle size. In Table 1 that follows, there is provided a listing of documents that disclose titanyl phthalocyanine polymorpic forms classified as belonging to one of the main types as indicated.
TABLE 1______________________________________Crystal OtherForm Names Documents______________________________________Type I β Toyo Ink Electrophotog. (Japan) 27,533 (1988) β Dainippon US 4,728,592 β Sanyo-Shikiso JOP 63-20365 A Mitsubishi JOP 62-25685, -6, -7 Conference Proceedings A Konica "Japan Hardcopy 1989", 103, (1989)Type II α Toyo Ink "Electrophoto (Japan)" 27,533 (1988) α Sanyo-Shikiso JOP 63-20365 α Konica US 4,898,799 α Dainippon US 4,728,592 α Mita EU 314,100 B Mitsubishi JOP 62-25685, -6, -7 B Konica "Japan Hardcopy 1989, 103, (1989)Type III C Mtsubishi OP 62-25685, -6, -7 C Konica "Japan Hardcopy 1989, 103, (1989) m Toyo Ink "Electrophoto (Japan)" 27,533 (1988)Type IV y Konica "Japan Hardcopy 1989", 103, (1989) Un- Konica US 4,898,799 named New Sanyo-Shikiso JOP 63-20365 Type______________________________________
More specifically, the aforementioned documents illustrate, for example, the use of specific polymorphs of TiOPc in electrophotographic devices. Three crystal forms of titanyl phthalocyanine, differentiated by their XRPDs, were specifically illustrated, identified as A, B, and C, which it is believed are equivalent to Types I, II, and III, respectively.
In Sanyo-Shikiso Japanese 63-20365/86, reference is made to the known crystal forms alpha and beta TiOPc (Types II and I, respectively, it is believed), which publication also describes a process for the preparation of a new form of titanyl phthalocyanine. This publication appears to suggest the use of the unnamed titanyl phthalocyanine as a pigment and its use as a recording medium for optical discs. This apparently new form was prepared by treating acid pasted TiOPc (Type II form, it is believed) with a mixture of chlorobenzene and water at about 50° C. The resulting apparently new form is distinguished on the basis of its XRPD, which appears to be identical to that shown in FIG. 1 for the Type IV polymorph.
In U.S. Pat. No. 4,728,592, there is illustrated, for example, the use of alpha type TiOPc (Type II) in an electrophotographic device having sensitivity over a broad wavelength range of from 500 to 900 nanometers. This form was prepared by the treatment of dichlorotitanium phthalocyanine with concentrated aqueous ammonia and pyridine at reflux for 1 hour. Also described in the aforementioned patent is a beta Type TiOPc (Type I) as a pigment, which is believed to provide a much poorer quality photoreceptor.
In Konica Japanese 64-17066/89, there is disclosed, for example, the use of a new crystal modification of TiOPc prepared from alpha type pigment (Type II) by milling it in a sand mill with salt and polyethylene glycol. This pigment has a strong XRPD peak at a value of 2 theta of 27.3 degrees. This publication also discloses that this new form differs from alpha type pigment (Type II) in its light absorption and shows a maximum absorbance at 817 nanometers compared to alpha-type, which has a maximum at 830 nanometers. The XRPD shown in the publication for this new form is believed to be identical to that of the Type IV form previously described by Sanyo-Shikiso in JOP 63-20365. The aforementioned Konica publication also discloses the use of this new form of TiOPc in a layered electrophotographic device having high sensitivity to near infrared light of 780 nanometers. The new form is indicated to be superior in this application to alpha type TiOPc (Type II). Further, this new form is also described in U.S. Pat. No. 4,898,799 and in a paper presented at the Annual Conference of Japan Hardcopy in July 1989. In this paper, this same new form is referred to as Type y, and reference is also made to Types I, II, and III as A, B, and C, respectively.
In the journal, Electrophotography (Japan) vol. 27, pages 533 to 538, Toyo Ink Manufacturing Company, there are disclosed, for example, alpha and beta forms of TiOPc (Types I and II, it is believed) and also this journal discloses the preparation of a Type m TiOPc, an apparently new form having an XRPD pattern which was distinct from other crystal forms. It is believed that his XRPD is similar to that for the Type III titanyl phthalocyanine pigment but it is broadened most likely as the particle size is much smaller than that usually found in the Type III pigment. This pigment was used to prepare photoreceptor devices having greater sensitivity at 830 nanometers than alpha or beta Type TiOPc (Type II or I, respectively).
Processes for the preparation of specific polymorphs of titanyl phthalocyanine, which require the use of a strong acid such as sulfuric acid, are known, and these processes, it is believed, are not easily scalable. One process as illustrated in Konica Japanese Laid Open on Jan. 20, 1989 as 64-17066 (U.S. Pat. No. 4,898,799 appears to be its equivalent), the disclosure of which is totally incorporated herein by reference, involves, for example, the reaction of titanium tetrachloride and phthalodinitrile in 1-chloronaphthalene solvent to produce dichlorotitanium phthalocyanine which is then subjected to hydrolysis by ammonia water to enable the Type II polymorph. This phthalocyanine is preferably treated with an electron releasing solvent such as 2-ethoxyethanol, dioxane, N-methylpyrrolidone, followed by subjecting the alpha-titanyl phthalocyanine to milling at a temperature of from 50° to 180° C. In a second method described in the aforementioned Japanese Publication, there is disclosed the preparation of alpha type titanyl phthalocyanine with sulfuric acid. Another method for the preparation of Type IV titanyl phthalocyanine involves the addition of an aromatic hydrocarbon, such as chlorobenzene solvent, to an aqueous suspension of Type II titanyl phthalocyanine prepared by the well-known acid pasting process, and heating the resultant suspension to about 50° C. as disclosed in Sanyo-Shikiso Japanese 63-20365, Laid Open in Jan. 28, 1988. In Japanese 171771/1986, Laid Open Aug. 2, 1986, there is disclosed the purification of metallophthalocyanine by treatment with N-methylpyrrolidone.
To obtain a TiOPc-based photoreceptor having high sensitivity to near infrared light, it is believed necessary to control not only the purity and chemical structure of the pigment, as is generally the situation with organic photoconductors, but also to prepare the pigment in the correct crystal modification. The disclosed processes used to prepare specific crystal forms of TiOPc, such as Types I, II, III and IV, are either complicated and difficult to control as in the preparation of pure Types I and II pigment by careful control of the synthesis parameters by the processes described in Mitsubishi Japanese 62-25685, -6 and -7, or involve harsh treatment such as sand milling at high temperature, reference Konica U.S. Pat. No. 4,898,799; or dissolution of the pigment in a large volume of concentrated sulfuric acid, a solvent which is known to cause decomposition of metal phthalocyanines, reference Sanyo-Shikiso Japanese 63-20365 and Mita EPO 314,100.
Generally, layered photoresponsive imaging members are described in a number of U.S. patents, such as U.S. Pat. No. 4,265,900, the disclosure of which is totally incorporated herein by reference, wherein there is illustrated an imaging member comprised of a photogenerating layer, and an aryl amine hole transport layer. Examples of photogenerating layer components include trigonal selenium, metal phthalocyanines, vanadyl phthalocyanines, and metal free phthalocyanines. Additionally, there is described in U.S. Pat. No. 3,121,006 a composite xerographic photoconductive member comprised of finely divided particles of a photoconductive inorganic compound dispersed in an electrically insulating organic resin binder. The binder materials disclosed in the '006 patent comprise a material which is incapable of transporting for any significant distance injected charge carriers generated by the photoconductive particles.
In a copending application U.S. Ser. No. 537,714 filed Jun. 14, 1990, the disclosure of which is totally incorporated herein by reference, there are illustrated photoresponsive imaging members with photogenerating titanyl phthalocyanine layers prepared by vacuum deposition. It is indicated in this copending application that the imaging members comprised of the vacuum deposited titanyl phthalocyanines and aryl amine hole transporting compounds exhibit superior xerographic performance as low dark decay characteristics result and higher photosensitivity is generated, particularly in comparison to several prior art imaging members prepared by solution coating or spray coating, reference for example, U.S. Pat. No. 4,429,029 mentioned hereinbefore.
In copending application U.S. Ser. No. 533,265 filed Jun. 4, 1990, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of phthalocyanine composites which comprises adding a metal free phthalocyanine, a metal phthalocyanine, a metalloxy phthalocyanine or mixtures thereof to a solution of trifluoroacetic acid and a monohaloalkane; adding to the resulting mixture a titanyl phthalocyanine; adding the resulting solution to a mixture that will enable precipitation of said composite; and recovering the phthalocyanine composite precipitated product.
In copending applications U.S. Ser. No. 683,935 filed Apr. 11, 1991 there is disclosed a process for the preparation of titanyl phthalocyanine which comprises the treatment of titanyl phthalocyanine Type X with a halobenzene; U.S. Ser. No. 678,506 filed Apr. 1, 1991 discloses a process for the preparation of titanyl phthalocyanine which comprises the reaction of a titanium tetraalkoxide and diiminoisoindolene in the presence of a halonaphthalene solvent; dissolving the resulting Type I titanyl phthalocyanine in a haloacetic acid and an alkylene halide; adding the resulting mixture slowly to a cold alcohol solution; and thereafter isolating the resulting Type X titanyl phthalocyanine with an average volume particle size diameter of from about 0.02 to about 0.5 micron; and Ser. No. 683,901 filed Apr. 11, 1991 discloses a process for the preparation of titanyl phthalocyanine Type I which comprises the reaction of titanium tetraalkoxide and diiminoisoindolene in the presence of a halonaphthalene solvent. The disclosures of each of the aforementioned copending patent applications are totally incorporated herein by reference.
SUMMARY OF THE INVENTION
It is a feature of the present invention to provide processes for the preparation of titanyl phthalocyanines with many of the advantages illustrated herein.
It is yet another feature of the present invention to provide economically scalable processes for the preparation of Type X titanyl phthalocyanines.
Another feature of the present invention relates to the preparation of stable titanyl phthalocyanine Type X polymorphs.
Further, another feature of the present invention relates to the preparation of photogenerating titanyl phthalocyanines Type X by the solubilization of titanyl phthalocyanine Type I followed by the reprecipitation into solvent compositions and washing with an organic solvent, for example fluorobenzene.
Moreover, another feature of the present invention relates to the preparation of stable titanyl phthalocyanine Type X with high purities, for example exceeding about 99 percent, by the treatment thereof with fluorobenzene, and the use thereof in electrophotographic imaging processes.
Yet another feature of the present invention is the provision of processes that affords a Type X crystal form of TiOPc with improved photosensitivity when selected as a photogenerator in a layered imaging member.
Another feature of the present invention in an embodiment thereof resides in the preparation of TiOPc Type X polymorphs having a small particle size of about 0.1 micron which is advantageous for the preparation of electrophotographic devices since, for example, the prepared polymorphs can be easily dispersed in coating compositions.
Yet another feature of the present invention is that mild conversion conditions can be selected, which do not cause decomposition of the titanyl phthalocyanine pigment.
A further feature of the present invention resides in the provision of photoresponsive imaging members with an aryl amine hole transport layer, and a photogenerator layer comprised of titanyl phthalocyanine pigment Type X obtained by the processes illustrated herein.
These and other features of the present invention are accomplished in embodiments thereof by the provision of processes for the preparation of titanyl phthalocyanines and photoresponsive imaging members thereof. More specifically, in one embodiment of the present invention there are provided processes for the preparation of titanyl phthalocyanine (TiOPc) Type X polymorphs which comprises the solubilization of a titanyl phthalocyanine Type I, which can be obtained by the reaction of Dl 3 and titanium tetrabutoxide in the presence of a solvent, such as chloronaphthalene, reference copending application U.S. Ser. No. 678,506 filed Apr. 1, 1991 the disclosure of which is totally incorporated herein by reference, in a mixture of trifluoroacetic acid and methylene chloride, precipitation of the desired titanyl phthalocyanine Type X, separation by, for example, filtration, and thereafter subjecting the product to washing with fluorobenzene. The product can be identified by various known means including X-ray powder diffraction (XRPD).
One embodiment of the present invention is directed to processes for the preparation of titanyl phthalocyanine Type X, which comprise the reaction of titanium tetrapropoxide with diiminoisoindolene in N-methylpyrrolidone solvent to provide Type I titanyl phthalocyanine as determined by X-ray powder diffraction; dissolving the resulting titanyl phthalocyanine in a mixture of trifluoroacetic acid and methylene chloride; adding the resulting mixture to a stirred organic solvent, such as methanol, water or mixtures thereof; separating the resulting precipitate of Type X by, for example, vacuum filtration through a glass fiber paper in a Buchner funnel; washing the obtained Type X pigment with an organic solvent, such as an aliphatic alcohol, with from about 1 to about 10 carbon atoms, like methanol; washing with water and then treating the titanyl phthalocyanine Type X product obtained with fluorobenzene.
Examples of titanyl phthalocyanine reactants that can be selected for the processes of the present invention in effective amounts of, for example, from about 1 weight percent to about 40 percent by weight of the trifluoroacetic acidic solvent mixture include known available titanyl phthalocyanines; titanyl phthalocyanines synthesized from the reaction of titanium halides such as titanium trichloride, titanium tetrachloride or tetrabromide; titanium tetraalkoxides such as titanium tetra-methoxide, -ethoxide, -propoxide, -butoxide, -isopropoxide and the like; and other titanium salts. These materials can be reacted with, for example, phthalonitrile and diiminoisoindolene in solvents such as 1-chloronaphthalene, quinoline, N-methylpyrrolidone, and alkylbenzenes such as xylene at temperatures of from about 120° to about 300° C. to provide Type I titanyl phthalocyanine.
As the solvent mixture for the Type I titanyl phthalocyanine, obtained as illustrated herein or obtained from other sources, there can be selected a strong organic acid, such as a trihaloacetic acids, including trifluoroacetic acid or trichloroacetic acid, and a cosolvent, such as an alkylene halide, such as methylene chloride, chloroform, trichloroethylene, bromoform and other short chain halogenated alkanes and alkenes with from 1 to about 6 carbon atoms and from 1 to about 6 halogen atoms including chlorofluorocarbons and hydrochlorofluorocarbons; haloaromatic compounds such as chlorobenzene, dichlorobenzene, chloronaphthalene, fluorobenzene, bromobenzene, and benzene; alkylbenzenes such as toluene and xylene; and other organic solvents which are miscible with strong organic acids and which will effectively dissolve the titanyl phthalocyanine in effective amounts of, for example, a ratio of from about 1 to 50 parts of acid to about 50 parts of cosolvent such as methylene chloride. In an embodiment of the present invention, a preferred solvent mixture is comprised of trifluoroacetic acid and methylene chloride in a ratio of from about 5 parts of acid to about 95 parts of methylene chloride to 25 parts of acid to 75 parts of methylene chloride.
Subsequent to solubilization with the above solvent mixture and stirring for an effective period of time of, for example, from about 5 minutes to about two weeks, the resulting mixture is added to a solvent that will enable precipitation of the desired titanyl phthalocyanine polymorph, such as Type X, which solvent is comprised of an alcohol such as an alkylalcohol including methanol, ethanol, propanol, isopropanol, butanol, n-butanol, pentanol and the like; ethers such as diethyl ether and tetrahydrofuran; hydrocarbons such as pentane, hexane and the like with, for example, from about 4 to about 10 carbon atoms; aromatic solvents such as benzene, toluene, xylene, halobenzenes such as chlorobenzene, and the like; carbonyl compounds such as ketones such as acetone, methyl ethyl ketone, and butyraldehyde; glycols such as ethylene and propylene glycol and glycerol; polar aprotic solvents such as dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone; water and mixtures thereof; followed by filtration of the titanyl phthalocyanine polymorph Type X, and washing with various solvents such as, for example, deionized water and an alcohol such as methanol and the like, which serves to remove residual acid and any impurities which might have been released by the process of dissolving and reprecipitating the pigment. The solid resulting can then be dried by, for example, heating yielding a dark blue pigment of the desired titanyl phthalocyanine Type X polymorph, as determined by XRPD analysis. The Type X obtained is then washed with fluorobenzene, and the stable product Type X with excellent photosensitivity separated therefrom by, for example, filtration.
In an embodiment of the present invention, there is provided a process for the preparation of titanyl phthalocyanine polymorph Type X, which comprises: 1) dissolving the precursor pigment, Type I titanyl phthalocyanine, in a mixture of trifluoroacetic acid and methylene chloride comprised of from 5 percent acid to about 25 percent acid and 95 parts to 75 parts of methylene chloride, wherein the amount of precursor pigment is, for example, from 5 parts to about 25 parts of the precursor pigment to 100 parts of acid solution by adding the pigment to the solution and stirring the mixture for an effective period of time, for example from about 5 minutes to about four weeks, and in an embodiment about two weeks, at a temperature of from about 0° to about 50° C.; 2) pouring or adding the resultant solution into a rapidly stirred precipitant solvent in a ratio of from about 1 part of the aforementioned pigment solution to 2 parts of precipitant solution to about 1 part pigment solution to about 50 parts of precipitant at a temperature of from about 0° to about 100° C. over a period of from 1 minute to about 60 minutes to ensure rapid efficient mixing in an embodiment, the precipitant solution was stirred at a rate sufficient to form a deep vortex in the reaction vessel, and the pigment was poured in a slow stream into the side of the vortex; 3) following the addition, the resultant dispersion of the polymorphic form Type X of TiOPc was stirred at a temperature of from 0° to about 100° C. for a period of from about 5 minutes to about 24 hours; 4) subsequently separating the titanyl phthalocyanine Type X from the mother liquor by filtration, for example through a glass fiber filter in a porcelain filter funnel, and washing the product titanyl phthalocyanine Type X pigment in the funnel with an effective amount of solvent, for example from about 20 parts of wash solvent to about 1 part of the starting pigment, such as methanol, to remove most of the acidic mother liquor; 5) redispersing the resulting wet cake in a solvent, such as methanol, acetone, water, and the like in an effective amount of, for example, from about 20 parts to about 100 parts of solvent to 1 part of the pigment for a period of from about 5 minutes to 24 hours at a temperature of from 0° C. to about 100° C., the primary purpose of such washing being to further remove any residual acid or other impurities from the Type X TiOPc which resulted from the precipitation process; 6) isolating the desired titanyl phthalocyanine polymorph Type X by, for example, filtration through a glass fiber filter as in step (4), and subsequently optionally washing the solid product in the funnel with a solvent, such as water methanol or acetone, and the like to complete purification. Subsequently, the Type X product is washed with fluorobenzene to provide Type X titanyl phthalocyanine having excellent xerographic characteristics, for example an E 1/2 equal to 1.1 ergs/cm 2 , a dark decay of 23 to 25 volts/second, and a discharge at 5 and 10 ergs/cm 2 of 85 and 89 percent, respectively, when the aforementioned Type X was selected as a photogenerator in a layered imaging member, such as that of Example III. The final product can be obtained after the solid has been dried at a temperature of from about 25° to about 150° C. for a time of 1 hour to about 24 hours, for example either in the air or under vacuum. A yield corresponding to about 95 percent to about 75 percent of the weight of the starting pigment can be obtained. The polymorphic form of the final pigment was determined by XRPD analysis, and was determined to be Type X, and remained as Type X after two months as determined by XRPD analysis.
A typical small scale conversion reaction was accomplished in an embodiment of the present invention as follows:
Two grams of titanyl phthalocyanine Type I synthesized by the process of Example I, below, was dissolved in 20 milliliters of a 1:4 mixture (V/V) of trifluoroacetic acid in methylene chloride by stirring in a 25 milliliter Erlenmeyer flask at room temperature for 5 minutes. The resultant dark green solution, which did not contain any undissolved material, was then poured into 200 milliliters of methanol in a 250 milliliter Erlenmeyer flask with vigorous stirring at room temperature. The resultant dark blue suspension was stirred at room temperature for an additional 30 minutes and then was filtered through a 4.25 centimeter glass fiber filter (Whatman GF/A grade) and the solid was washed on the funnel with about 20 milliliters of methanol. The resultant wet filter cake was transferred to a 125 milliliter flask and was redispersed in 50 milliliters of methanol. The resulting dispersion was stirred for 30 minutes, then was refiltered as above, and the solid resulting was washed on the funnel with methanol (20 milliliters) then water (2×20 milliliters) and finally with methanol again (20 milliliters). Subsequently, the Type X titanyl phthalocyanine obtained was then washed with fluorobenzene as illustrated herein, and the Type X separated therefrom by, for example, filtration. The solid was dried at 70° C. for 2 hours to yield about 2 grams of dark blue pigment. The product was identified as Type X TiOPc on the basis of its XRPD trace.
In another embodiment of the present invention, solutions of TiOPc Type I in a 1:4 mixture of trifluoroacetic acid and methylene chloride were precipitated into varying mixtures of methanol and water as indicated in the Table that follows, followed by washing with fluorobenzene as illustrated herein. The titanyl phthalocyanine Type X products obtained were analyzed and identified by XRPD traces.
TABLE 2______________________________________PrecipitantSolvent RatioMeOH/H.sub.2 O XRPD Analysis______________________________________100:0 Type Z-195:5 Type III (major)90:10 Type III (major)85:15 Type III (major)80:20 Type III (major)75:25 Type III (major)70:30 Type III (major)65:35 Type III (minor) + Type X60:40 Type X55:45 Type X50:50 Type X45:55 Type X40:60 Type X35:65 Type X30:70 Type IV25:75 Type IV20:80 Type IV 0:100 Type IV______________________________________ The data in this Table illustrate that at relatively high methanol concentrations the preponderant polymorph formed is the Type III form. However, beginning at a composition of about 65 percent of methanol and 35 percent of water, the Type X form predominates. Polymorphically pure Type X can be obtained when the acid solution is precipitated into methanol/water compositions with, for example, from 60 to 35 percent of methanol. Compositions containing less than about 35 percent of methanol and pure water result in the formation of the Type IV form which has the XRPD peaks at 2 theta=9.8 degrees.
Another embodiment of the present invention is directed to a process for the preparation of titanyl phthalocyanine Type X, which comprises the reaction of diiminoisoindolene in a ratio of from 3 to 5 molar equivalents with 1 molar equivalent of titanium tetrapropoxide in chloronaphthalene or N-methylpyrrolidone solvent in a ratio of from about 1 part diiminoisoindolene to from about 5 to about 10 parts of solvent. These ingredients are stirred and warmed to a temperature of from about 160° to 240° C. for a period of from about 30 minutes to about 8 hours. The reaction mixture is then cooled to a temperature of from about 100° to 160° C., and the resulting mixture is filtered through a sintered glass funnel (M porosity). The pigment obtained is then washed in the funnel with boiling dimethyl formamide (DMF) solvent in an amount which is sufficient to remove all deeply colored impurities from the solid as evidenced by a change in the color of the filtrate from an initial black color to a faint blue green. Following this, the pigment is stirred in the funnel with boiling DMF in a sufficient quantity to form a loose suspension, which is refiltered. The solid is finally washed with DMF at room temperature, then with a small amount of methanol and is dried at about 70° C. for from about 2 to about 24 hours. Generally, an amount of DMF equal to the amount of solvent (chloronaphthalene or N-methylpyrrolidone) used in the synthesis reaction is required for the washing step. Thereafter, the Type I titanyl phthalocyanine pigment obtained is dissolved in trifluoroacetic acid and methylene chloride, re-precipitated in a methanol and water solution, washed with organic solvents such as methanol or water or the like, and the Type X obtained is then washed with fluorobenzene as illustrated herein. The yield from this synthesis is from 60 to about 80 percent. X-ray powder diffraction, XRPD, analysis of the product thus obtained indicated that it was the Type X polymorph of titanyl phthalocyanine.
Numerous different layered photoresponsive imaging members with the phthalocyanine pigments obtained by the processes of the present invention can be fabricated. In one embodiment, thus the layered photoresponsive imaging members can be comprised of a supporting substrate, a charge transport layer, especially an aryl amine hole transport layer, and situated therebetween a photogenerator layer comprised of titanyl phthalocyanine of Type X. Another embodiment of the present invention is directed to positively charged layered photoresponsive imaging members comprises of a supporting substrate, a charge transport layer, especially an aryl amine hole transport layer, and as a top overcoating titanyl phthalocyanine pigments Type X obtained with the processes of the present invention. Moreover, there is provided in accordance with the present invention an improved negatively charged photoresponsive imaging member comprised of a supporting substrate, a thin adhesive layer, a titanyl phthalocyanine obtained by the processes of the present invention photogenerator dispersed in a polymeric resinous binder, and as a top layer aryl amine hole transporting molecules dispersed in a polymeric resinous binder.
The photoresponsive imaging members of the present invention can be prepared by a number of known methods, the process parameters and the order of coating of the layers being dependent on the member desired. The imaging members suitable for positive charging can be prepared by reversing the order of deposition of photogenerator and hole transport layers. The photogenerating and charge transport layers of the imaging members can be coated as solutions or dispersions onto selective substrates by the use of a spray coater, dip coater, extrusion coater, roller coater, wire-bar coater, slot coater, doctor blade coater, gravure coater, and the like, and dried at from 40° to about 200° C. for from 10 minutes to several hours under stationary conditions or in an air flow. The coating is carried out in such a manner that the final coating thickness is from 0.01 to about 30 microns after it has dried. The fabrication conditions for a given layer will be tailored to achieve optimum performance and cost in the final device.
Imaging members with the titanyl phthalocyanine pigments of the present invention are useful in various electrostatographic imaging and printing systems, particularly those conventionally known as xerographic processes. Specifically, the imaging members of the present invention are useful in xerographic imaging processes wherein the titanyl phthalocyanines pigments absorb light of a wavelength of from about 600 nanometers to about 900 nanometers. In these known processes, electrostatic latent images are initially formed on the imaging member followed by development, and thereafter transferring the image to a suitable substrate.
Moreover, the imaging members of the present invention can be selected for electronic printing processes with gallium arsenide light emitting diode (LED) arrays which typically function at wavelengths of from 660 to about 830 nanometers.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention and further features thereof, reference is made to the following detailed description of various preferred embodiments wherein:
FIGS. 1A, 1B, 1C, 1D and 1E are diffractograph summaries of the XRPDs of the known polymorphs, Type I, II, III, IV, and X of titanyl phthalocyanine;
FIG. 5 is a partially schematic cross-sectional view of a negatively charged photoresponsive imaging member of the present invention; and
FIG. 6 is a partially schematic cross-sectional view of a positively charged photoresponsive imaging member of the present invention.
DESCRIPTION OF EMBODIMENTS
Illustrated in FIG. 5 is a negatively charged photoresponsive imaging member of the present invention comprised of a supporting substrate 1, a solution coated adhesive layer 2 comprised, for example, of a polyester 49,000 available from Goodyear Chemical, a photogenerator layer 3 comprised of titanyl phthalocyanine Type X, obtained with the process of the present invention, optionally dispersed in an inactive resinous binder, and a charge transport layer 5 comprised of N,N'-diphenyl-N,N'-bis(3-methyl phenyl)-1,1'-biphenyl-4,4'-diamine, dispersed in a polycarbonate resinous binder 7.
Illustrated in FIG. 6 is a positively charged photoresponsive imaging member of the present invention comprised of a substrate 10, a charge transport layer 12 comprised of N,N'-diphenyl-N,N'-bis(3-methyl phenyl)-1,1'-biphenyl-4,4'-diamine dispersed in a polycarbonate resinous binder 14, and a photogenerator layer titanyl phthalocyanine Type X, 16 obtained with the process of the present invention, optionally dispersed in an inactive resinous binder 18.
Substrate layers selected for the imaging members of the present invention can be opaque or substantially transparent, and may comprise any suitable material having the requisite mechanical properties. Thus, the substrate may comprise a layer of insulating material including inorganic or organic polymeric materials, such as MYLAR® a commercially available polymer, MYLAR® containing titanium, a layer of an organic or inorganic material having a semiconductive surface layer such as indium tin oxide or aluminum arranged thereon, or a conductive material inclusive of aluminum, chromium, nickel, brass or the like. The substrate may be flexible, seamless, or rigid and many have a number of many different configurations, such as for example a plate, a cylindrical drum, a scroll, an endless flexible belt and the like. In one embodiment, the substrate is in the form of a seamless flexible belt. In some situations, it may be desirable to coat on the back of the substrate, particularly when the substrate is a flexible organic polymeric material, an anticurl layer, such as for example polycarbonate materials commercially available as MAKROLON®.
The thickness of the substrate layer depends on many factors, including economical considerations, thus this layer may be of substantial thickness, for example over 3,000 microns, or of minimum thickness providing there are no adverse effects on the system. In one embodiment, the thickness of this layer is from about 75 microns to about 300 microns.
With further regard to the imaging members, the photogenerator layer is preferably comprised of the titanyl phthalocyanine pigments Type X obtained with the processes of the present invention dispersed in resinous binders. Generally, the thickness of the photogenerator layer depends on a number of factors, including the thicknesses of the other layers and the amount of photogenerator material contained in this layer. Accordingly, this layer can be of a thickness of from about 0.05 micron to about 10 microns when the titanyl phthalocyanine photogenerator composition is present in an amount of from about 5 percent to about 100 percent by volume. In one embodiment, this layer is of a thickness of from about 0.25 micron to about 1 micron when the photogenerator composition is present in this layer in an amount of 30 to 75 percent by volume. The maximum thickness of this layer in an embodiment is dependent primarily upon factors, such as photosensitivity, electrical properties and mechanical considerations. The charge generator layer can be obtained by dispersion coating the TiOPc obtained with the processes of the present invention, and a binder resin with a suitable solvent. The binder may be omitted. The dispersion can be prepared by mixing and/or milling the TiOPc in equipment such as paint shakers, ball mills, sand mills and attritors. Common grinding media such as glass beads, steel balls or ceramic beads may be used in this equipment. A binder resin may be selected from a wide number of polymers such as poly(vinyl butyral), poly(vinyl carbazole), polyesters, polycarbonates, poly(vinyl chloride), polyacrylates and methacrylates, copolymers of vinyl chloride and vinyl acetate, phenoxy resins, polyurethanes, poly(vinyl alcohol), polyacrylonitrile, polystyrene, and the like. The solvents to dissolve these binders depend upon the particular resin. In embodiments of the present invention, it is desirable to select solvents that do not effect the other coated layers of the device. Examples of solvents useful for coating TiOPc dispersions to form a photogenerator layer are ketones, alcohols, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, amines, amides, esters, and the like. Specific examples are cyclohexanone, acetone, methyl ethyl ketone, methanol, ethanol, butanol, amyl alcohol, toluene, xylene, chlorobenzene, carbon tetrachloride, chloroform, methylene chloride, trichloroethylene, tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, dimethylacetamide, butyl acetate, ethyl acetate, methoxyethyl acetate, and the like.
The coating of the TiOPc dispersion in embodiments of the present invention can be accomplished with spray, dip or wire bar methods such that the final dry thickness of the charge generator layer is from 0.01 to 30 microns and preferably from 0.1 to 15 microns after being dried at 40° to 150° C. for 5 to 90 minutes.
Also, illustrative examples of polymeric binder resinous materials that can be selected for the photogenerator pigment include those polymers as disclosed in U.S. Pat. No. 3,121,006, the disclosure of which is totally incorporated herein by reference.
As adhesives, there can be selected various known substances inclusive of polyesters, polyamides, poly(vinyl butyral), poly(vinyl alcohol), polyurethane and polyacrylonitrile. This layer is of a thickness of from about 0.05 micron to 1 micron. Optionally, this layer may contain conductive and nonconductive particles such as zinc oxide, titanium dioxide, silicon nitride, carbon black, and the like to provide, for example, in embodiments of the present invention desirable electrical and optical properties.
Aryl amines selected for the charge transporting layer which generally is of a thickness of from about 5 microns to about 75 microns, and preferably of a thickness of from about 10 microns to about 40 microns, include molecules of the following formula: ##STR1## dispersed in a highly insulating and transparent organic resinous binder wherein X is an alkyl group or a halogen, especially those substituents selected from the group consisting of (ortho) CH 3 , (para) CH 3 , (ortho) Cl, (meta) Cl, and (para) Cl.
Examples of specific aryl amines are N,N'-diphenyl-N,N'-bis(alkylphenyl)-1,1-biphenyl-4,4'-diamine wherein alkyl is selected from the group consisting of methyl, such as 2-methyl, 3-methyl and 4-methyl, ethyl, propyl, butyl, hexyl, and the like. With chloro substitution, the amine is N,N'-diphenyl-N,N'-bis(halo phenyl)-1,1'-biphenyl-4,4'-diamine wherein halo is 2-chloro, 3-chloro or 4-chloro. Other known hole transporting compounds can be selected.
Examples of the highly insulating and transparent resinous material or inactive binder resinous material for the transport layers include materials such as those described in U.S. Pat. No. 3,121,006, the disclosure of which is totally incorporated herein by reference. Specific examples of organic resinous materials include polycarbonates, acrylate polymers, vinyl polymers, cellulose polymers, polyesters, polysiloxanes, polyamides, polyurethanes and epoxies as well as block, random or alternating copolymers thereof. Preferred electrically inactive binders are comprised of polycarbonate resins having a molecular weight of from about 20,000 to about 100,000 with a molecular weight of from about 50,000 to about 100,000 being particularly preferred. Generally, the resinous binder contains from about 10 to about 75 percent by weight of the active material corresponding to the foregoing formula, and preferably from about 35 percent to about 50 percent of this material.
Also, included within the scope of the present invention are methods of imaging and printing with the photoresponsive devices illustrated herein. These methods generally involve the formation of an electrostatic latent image on the imaging member, followed by developing the image with a toner composition, reference U.S. Pat. Nos. 4,560,635; 4,298,697 and 4,338,390, the disclosures of which are totally incorporated herein by reference, subsequently transferring the image to a suitable substrate, and permanently affixing the image thereto. In those environments wherein the device is to be used in a printing mode, the imaging method involves the same steps with the exception that the exposure step can be accomplished with a laser device or image bar.
The invention will now be described in detail with reference to specific preferred embodiments thereof, it being understood that these examples are intended to be illustrative only. The invention is not intended to be limited to the materials, conditions, or process parameters recited herein, it being noted that all parts and percentages are by weight unless otherwise indicated. Comparative data and Examples are also presented.
EXAMPLE I
Synthesis of Type I Titanyl Phathalocyanine
To a 300 milliliter three-necked flask fitted with mechanical stirrer, condenser and thermometer maintained under an argon atmosphere was added 32.7 grams (grams) (0.225 mole) of 1,3-diiminoisoindolene, 170 milliliters of N-methyl pyrrolidone and 15.99 grams (0.056 mole) of titanium tetrapropoxide (all the aforementioned reagents are available from Aldrich Chemical Company). The resulting mixture was stirred and warmed to reflux (about 198° C.) for 2 hours. The resultant black suspension was cooled to about 160° C. then was filtered by suction through a 350 milliliter M-porosity sintered glass funnel which had been preheated with boiling dimethyl formamide (DMF). The solid resulting was washed with two 150 milliliter portions of boiling DMF and the filtrate, initially black, became a light blue-green color. The solid was slurried in the funnel with 150 milliliters of boiling DMF and the suspension was filtered. The resulting solid was washed in the funnel with 150 milliliters of DMF at 25° C. then with 50 milliliters of methanol. The resultant shiny dark blue solid was dried at 70° C. overnight to yield 17.4 grams (54 percent) of pigment which was identified as Type I TiOPc on the basis of its XRPD. The elemental analysis of the product was: C, 66.44; H, 2.62; N, 20.00; Ash (TiO 2 ), 12.35. TiOPc requires: C, 66.67; H, 2.80; N, 19.44; Ash, 13.86.
EXAMPLE II
Synthesis of Type I Titanyl Phthalocyanine
A 1 liter three-necked flask fitted with mechanical stirrer, condenser and thermometer maintained under an atmosphere of argon was charged with diiminoisoindolene (94.3 grams, 0.65 mole), titanium tetrabutoxide (55.3 grams, 0.1625 mole; Aldrich) and 650 milliliters of 1-chloronaphthalene. The mixture was stirred and warmed. At about 140° C., the mixture turned dark green and began to reflux. At this time the condenser was removed and the vapor (this was identified as n-butanol by gas chromatography) was allowed to escape until the reflux temperature reached 230° C. The reaction was maintained at about this temperature for one and one half hours then was cooled to 15° C. Filtration using a 1 liter sintered glass funnel and washing with boiling DMF, then methanol, as in Example I provided 69.7 grams (74 percent yield) of blue pigment which was identified as Type I TiOPc by XRPD.
The elemental analysis of the product was: C, 67.38; H, 2.78; N, 19.10; Ash, 13.61. TiOPC requires: C, 66.67; H, 2.80; N, 19.44; Ash, 13.61.
EXAMPLE III
The titanyl phthalocyanines Type X were evaluated as photogenerators in xerographic imaging devices which were prepared by the following procedure. An aluminized Mylar substrate (4 mil) was coated with a Nylon 8 solution, prepared by dissolving 5 grams of Nylon 8 (Dainippon Ink and Chemical Company) in 16 grams of n-butanol, 24 grams of methanol and 4 grams of water using a 1 mil gap applicator. This layer was dried at 135° C. for 20 minutes; the final thickness was measured to be 0.6 micron. A dispersion of the TiOPc was prepared by ball milling 0.35 gram of the TiOPc, Type X, and poly(vinyl butyral) in 13.4 grams of butyl acetate in a 30 milliliter jar containing 70 grams of 1/8 inch stainless steel balls. The dispersion was milled for 20 hours then was coated onto the Nylon 8 layer described above using a 1 mil applicator. The thus formed photogenerating layer was dried at 100° C. for 10 minutes; its final thickness was determined to be about 0.40 micron.
Hole transporting layer solutions were prepared by dissolving 5.4 grams of N,N'-diphenyl-N,N-bis(3-methyl phenyl)-1,1'-biphenyl-4,4'-diamine, 8.1 grams of polycarbonate in 57.6 grams of chlorobenzene. The solution was coated onto the TiOPc generator layer using an 8 mil film applicator. The charge transporting layer thus obtained was dried at 115° C. for 60 minutes to provide a final thickness of about 23 microns.
The xerographic electrical properties of the photoresponsive imaging members were determined by electrostatically charging the surface thereof with a corona discharge source until the surface potential as measured by a capacitatively coupled probe attached to an electrometer attained an initial dark value, V 0 , of -800 volts. After resting for 0.5 second in the dark, the charged member reached a surface potential, V ddp , or dark development potential. The member was then exposed to filtered light from a Xenon lamp. A reduction in surface potential from V ddp to a background potential, V bg , due to the photodischarge effect was observed. The dark decay in volts per second was calculated as (V 0 -V ddp )/0.5. The percent of photodischarge was calculated as 100×(V ddp -V bg )/V ddp . The half-exposure energy, E 1/2 , the required exposure energy causing reduction of the V ddp to half of its initial value, was determined. The wavelength of light selected was 800 nanometers.
EXAMPLE IV
Preparation of Type X Titanyl Phthalocyanine
To a solution of trifluoroacetic acid (4 milliliters) in methylene chloride (16 milliliters) stirred with a magnet in a 50 milliliters Erlenmeyer flask was added 2 grams of Type I TiOPc, synthesized as in Example II, over a 10 second period. No heat was evolved and the resultant dark green solution, which contained no undissolved material, was stirred at room temperature for 5 minutes. The solution was poured over a 1 minute period into a solution of methanol (100 milliliters) and water (100 milliliters) contained in a 250 milliliter Erlenmeyer flask, which was stirred with a 25 millimeters long magnetic stir bar at a rate which was sufficient to create a vortex, which extended almost to the bottom of the flask. Following the addition, the resultant blue suspension was stirred at room temperature for 45 minutes, then was allowed to stand undisturbed for 25 minutes. The yellowish brown supernatant liquid was almost completely separated from the precipitated solid by carefully decanting the reaction vessel. The remaining blue residue was redispersed in 100 milliliters of methanol by stirring with a magnet for 1 hour at room temperature (about 25° C. throughout). The resultant suspension was filtered through a 7 centimeter diameter glass fiber filter in a porcelain filter funnel. It was then redispersed in 100 milliliters hot (>90° C.) of water and filtered again. This hot water wash was repeated until the conductivity of the filtrate was measured with a laboratory cell fixture with electrodes to be less than 20 μS. The product Type X phthalocyanine was then re-dispersed in 100 milliliters of fluorobenzene by stirring for 15 minutes. The solution was then filtered as illustrated herein, and dried at 75° C. overnight (18 hours) to provide 1.7 grams (85 percent yield) of dark blue pigment which was identified as Type X TiOPc by XRPD.
The resulting Type X pigment was selected for use as a photogenerator in the layered imaging member of Example III, evidencing a dark decay of 23 to 25 volts per second, and an E 1/2 of 1.1 ergs/cm 2 . Discharge at 5 and 10 ergs/cm 2 was 85 and 89 percent, respectively.
EXAMPLE V
Preparation of Type X Titanyl Phthalocyanine
To a solution of trifluoroacetic acid (4 milliliters) in methylene chloride (16 milliliters) stirred with a magnet in a 50 milliliter Erlenmeyer flask was added 2 grams of Type I TiOPc, synthesized as in Example II, over a 10 second period. No heat was evolved and the resultant dark green solution, which contained no undissolved material, was stirred at room temperature for 5 minutes. The solution was poured over a 1 minute period into a solution of methanol (100 milliliters) and water (100 milliliters) contained in a 250 milliliter Erlenmeyer flask, which was stirred with a 25 millimeters long magnetic stir bar at a rate which was sufficient to create a vortex, which extended almost to the bottom of the flask. Following the addition, the resultant blue suspension was stirred at room temperature for 45 minutes, then was allowed to stand undisturbed for 25 minutes. The yellowish brown supernatant liquid was almost completely separated from the precipitated solid by carefully decanting the reaction vessel. The remaining blue residue was redispersed in 100 milliliters of methanol by stirring with a magnet for 1 hour at room temperature. The resultant suspension was filtered through a 7 centimeter diameter glass fiber filter in a porcelain filter funnel. It was then redispersed in 100 milliliters of hot (>90° C.) water and filtered again. This hot water wash was repeated until the conductivity of the filtrate was measured to be less than 20 μS. The product Type X phthalocyanine was then dried at 75° C. overnight (18 hours) to provide 1.7 grams (85 percent yield) of dark blue pigment which was identified as Type X TiOPc by XRPD.
The resulting Type X pigment was selected for use as a photogenerator in the layered imaging member of Example III, evidencing a dark decay of 26 to 30 volts per second, and an E 1/2 of 1.4 ergs/cm 2 . Discharge at 5 and 10 ergs/cm 2 was 82 and 87 percent, respectively.
Other modifications of the present invention may occur to those skilled in the art subsequent to a review of the present application. The aforementioned modifications, including equivalents thereof are intended to be included within the scope of the present invention.
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A process for the preparation of titanyl phthalocyanine Type X which comprises dissolving titanyl phthalocyanine Type I in a solution of trifluoroacetic acid and methylene chloride; adding the resultant solution to a solvent enabling precipitation of Type X titanyl phthalocyanine; separating the titanyl phthalocyanine Type X from the solution; followed by a first washing with an organic solvent and a second washing with water; and thereafter a solvent treatment with fluorobenzene.
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RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 61/415,317 filed on Nov. 18, 2010.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to electrical harness testing and, more particularly, to methods for efficient distribution of equipment and adapters for testing.
[0004] 2. Description of the Related Art
[0005] Automated wiring harness test systems have long been known and widely used in aerospace and other industries for testing electrical harnesses and related subassemblies. In many cases the distribution of the termination points in the unit under test (UUT), which includes the wire harness or the electrical assembly up to and including a complete aircraft system, for example, is physically large. In such applications, the test stimulus and measurement switching hardware is often placed in multiple enclosures that are remote from the test system control hardware and closer to the UUT connections. Thus, it has been necessary for the test engineer to determine the best locations for the switching hardware by means of trial and error.
[0006] The connections between the UUT connectors and the tester switching units (SUs) are made using wire harnesses dedicated to the test process known as test adapter cables (TACs) or other similar terms such as harness adapter cables, etc.
[0007] Various computer assisted design (CAD) tools have been developed that can determine the specific routing of harnesses given known physical locations of the end connectors on the harnesses. While such tools may be applied to TAC design, the user must first determine the location of the tester units. However, since the placement of the tester units is dependent on the “best fit” of the TACs to the various tester units, this creates a design impasse that can result in a less than optimal test system layout.
[0008] Still other tools have been designed for generating test data and designing the test adapter cabling. However, these tools do not provide physical routing information. Rather, they require the user to determine the needed cable lengths independent of the tool and input that information as a parameter for the cable design.
[0009] Thus, there is a need for methods/systems capable of designing the layout of the tester system and determining the lengths of the TACs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a diagram of switching unit and adapter placement according to an embodiment of the present invention.
[0011] FIG. 2 is a diagram of switching unit and adapter placement according to an embodiment of the present invention.
[0012] FIG. 3 is a diagram of switching unit and adapter placement according to an embodiment of the present invention.
[0013] FIG. 4 is a diagram of switching unit and adapter placement according to an embodiment of the present invention.
[0014] FIG. 5 is a perspective view of a portion of an aircraft fuselage and various elements therein according to an embodiment of the present invention.
[0015] FIG. 6 is a plan view of a switching unit and several adapter connectors according to an embodiment of the present invention.
[0016] FIG. 7 is a flow chart showing a method of determining the arrangement of a plurality of SUs and a plurality of UUT connectors within an aircraft fuselage according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Embodiments of the invention are described herein with reference to schematic illustrations. As such, the actual shapes of elements are not represented, and variations from the shapes of the illustrations are expected. Thus, the elements illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region of a device and are not intended to limit the scope of the invention.
[0018] It is understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. Furthermore, relative terms such as “inner”, “outer”, “upper”, “above”, “lower”, “beneath”, and “below”, and similar terms, may be used herein to describe a relationship of one element to another. It is understood that these terms are intended to encompass different orientations in addition to the orientation depicted in the figures.
[0019] Although the ordinal terms first, second, etc., may be used herein to describe various objects, components, regions and/or sections, these objects, components, regions, and/or sections should not be limited by these terms. These terms are only used to distinguish one object, component, region, or section from another. Thus, unless expressly stated otherwise, a first object, component, region, or section discussed below could be termed a second object, component, region, or section without departing from the teachings of the present invention.
[0020] It will be understood that although embodiments of methods described herein are described as comprising various steps, these steps should not be limited to any particular order unless expressly stated otherwise or logically required.
[0021] Embodiments of the present invention provide methods/systems for determining a test system layout and simultaneously determining the test adapter cable lengths via a point clustering technique. In many embodiments of the invention, a modified K-Means clustering algorithm is used. However, it is understood by those skilled in the art that many other clustering algorithms can be utilized to achieve a similar result.
[0022] In one embodiment, a three-dimensional X-Y-Z coordinate system mapping the UUT mating connector locations is utilized to determine an optimized location for each SU and the UUT mating connectors that should be assigned to each SU. Given the determined SU location and the UUT connector location, the lengths of the various test adapter cables can also be calculated.
[0023] One coordinate system convention often used for vehicles, including aircraft, is based on an X-Y-Z system. The coordinate systems are discussed herein with a focus on aircraft, although it is understood that the coordinate system can be applied to many different vehicles and, indeed, other spaces not related to vehicles such as the interior space of a building, for example. Indeed, in a general sense, embodiments of the present invention may be used to arrange any associated objects (e.g., first- and second-type objects) within any 3D space.
[0024] In the particular case of an aircraft system, the X-axis is positive pointing aft and is typically called the station line or fuselage station (FS). The origin, or “0 station” is either at the nose of the aircraft, or more often, at some arbitrary point forward of the nose such that future extensions of the airframe do not cause the nose to extend past 0 into negative station numbers. The Y-axis is usually called the butt line (BL) with the origin being at the centerline of the vehicle and positive pointing toward the aircraft's right wing and negative toward the left wing. The Z-axis is known as the water line (WL) and is positive pointing upward. As with the station, the origin is either at ground level (with the landing gear in the down position) or more often, an arbitrary distance below the extended landing gear. In the United States, the distances are typically shown in inches. However, embodiments of the invention can operate on unitless coordinates since, as long as all dimensional data is provided in the same unit of measure, the units can be ignored for calculation purposes.
[0025] In many cases, named zones are provided rather than dimensional coordinates in indicating the location of components within the UUT. A separate listing of the physical location of each zone is provided to the test engineers. While, for the purpose of clarity, only the X-Y-Z coordinate system shall be detailed here, other embodiments allow for the use of a mapping lookup table that converts named zones to their respective X-Y-Z locations.
[0026] In some embodiments, a modified K-Means clustering algorithm is used to determine the assignment of UUT end connectors to each tester SU as well as to determine the location of the SUs. However, as noted herein it is understood by those skilled in the art that many other clustering algorithms can be utilized to achieve a similar result.
[0027] A K-Means clustering algorithm is particularly suited to embodiments of the present invention. It is understood that various limitations of K-Means clustering when used in other applications prove to be either of minor significance, or even advantageous, in its application to embodiments discussed herein. Specifically, the following limitations have been discussed in academic literature regarding K-Means clustering.
[0028] One often-cited limitation is that the algorithm depends on the initial choices for the cluster centers. This is of minor significance since the number of tester units is generally quite small and, due to the speed of the algorithm, the user has an opportunity to test various possible initial conditions.
[0029] Another consideration is that outlying points will have a large effect on the center of the cluster. This actually proves to be an advantage because, rather than attempting to create patterns, one important goal is to minimize the total test cable length. Using the mean of the cluster rather than, for example, a median connector in the cluster provides a better solution.
[0030] Another cited limitation is that K-Means techniques do not recognize patterns in the items being clustered. While disadvantageous in some other applications, this feature of a K-Means algorithm is useful as the goal is to minimize cable lengths rather than to create clusters of like items. However, in some embodiments of the invention, a “weight factor” can be added for attributes such as aircraft zone names. This would allow grouping of connectors by zone when practical.
[0031] In some applications, K-Means is not massively scalable since the number of calculations increases exponentially with the number of items and/or clusters. However, in application to embodiments of the present invention this limitation has no practical impact because the number of UUT connectors in even the most complex aircraft is less than 10 4 while the number of tester units is less than 10 3 , both of which are relatively small quantities when compared to the number of items in other kinds of systems.
[0032] Some embodiments of the invention comprise an input module configured to receive as input the locations of the UUT end connectors as well as an initial placement of the test system SUs. The distance from each UUT end connector to each SU is then calculated and the UUT connectors are temporarily assigned to the closest SU. The difference between the distance to the nearest SU and the next nearest SU is also recorded for each UUT connector for possible use in further calculations. All of these calculations can be done, for example, in a calculation module.
[0033] Since each SU has a finite capacity (i.e., a maximum number of available connections), there may be more UUT connectors assigned than can be accommodated. The connectors that have the smallest delta distance between the nearest and next nearest SU are transferred to the next nearest SU if that unit is not at or above its own capacity. The transfers continue until the first unit is within its capacity. Then the other SUs are tested for exceeding capacity, and the process is repeated. This process is not reiterative since it is possible that there are more UUT connections than the total capacity of all SUs, and, given that the overall algorithm is reiterative, at no point should it assume that the SU locations are final. In some embodiments, named zones can be used to ensure that all connectors in a single zone are moved as a group from one SU to another.
[0034] Once all the UUT connectors have been assigned to an SU, each SU is relocated to the center (centroid) of the cluster of all UUT connectors assigned to it.
[0035] The complete algorithm is then repeated recursively until no SUs require significant movement to be placed in the center of the clusters.
[0036] The user may then manually adjust the final SU locations to account for various practical limitations to their placement, such as the positioning of work platforms or obstacles, for example. Manual adjustments can occur in two stages. In the first stage, the UUT connector assignments are recalculated to assign connectors to the nearest SU. In the second stage, the user indicates that they are satisfied with the assignments and further SU movement simply recalculates the distance to the assigned unit without reassignment of any connectors to any other SU.
[0037] In most instances, the SU test adapter connectors themselves have a finite number of contacts which limit the number of UUT connectors assigned to them. Thus, the embodiments of the method can be applied at a more granular level to the connections to each connector on each SU just as it is applied to each SU within the test system as a whole.
[0038] Embodiments also include processing of physical obstacles in the UUT such as, for example, floors, walls and bulkheads that do not allow cables to pass from one side to the other. Other physical limitations may also be accounted for. In one embodiment, UUT connectors are only allowed to be assigned to SUs that are on the same side of all obstacles as themselves.
[0039] In one embodiment of the invention, obstacles are assumed to be infinite planes parallel to the X, Y or Z axes. However, it is clear to one of skill in the art that more complex obstacle geometries are possible such as 2-D or 3-D polygons and 3-D surfaces such as, for example, conical sections and spherical sections.
[0040] Some embodiments may utilize “taxicab geometry.” In taxicab geometry distances are measured based on following a strict X-Y grid rather than a straight line potentially crossing a diagonal vector. This geometry is so named as a taxicab moving from one point in a city to another must follow the grid of streets rather than cutting across the middle of the city blocks. Taxicab geometry may also be applied to 3-dimensional space by following only lines parallel to the X, Y, and Z axes. In this particular embodiment, the final distances between UUT connectors and SUs is calculated using taxicab geometry in order to account for the physical constraints of routing electrical cables across floors and vertically rather than creating an inaccessible array of cables routed in all directions. This also allows for additional cable length that may be necessary to route around physical obstacles that might appear in the test environment.
[0041] Various embodiments of the invention provide for user control and reporting either by tables of X-Y-Z coordinates or in a graphical representation of the 3D model. Embodiments of the present invention may be embodied in a computer readable medium or in pre-programmed hardware.
[0042] As shown in FIGS. 1 , 2 , 3 , 4 and 7 some embodiments of the present invention utilize the K-Means clustering technique to optimize the positioning of test equipment switching units (SUs) 1 , 2 and 3 relative to the UUT connectors as represented by the items 4 , 5 and 6 .
[0043] FIG. 1 represents an initial estimate as to the positioning of the SUs 1 , 2 , 3 . While the initial positions are not critical, this placement will have an impact on the final results. In FIG. 2 , the UUT connectors 4 , 5 , 6 are initially assigned to the nearest SU as represented by the connection lines 7 and 8 . The determination of the nearest SU to a UUT connector is determined by calculating the straight line distance from the UUT connector to each SU using the following formula:
[0000] d=|x un −x sua |+|y un −y sua |+|z un −z sua |
[0000] Where, d is the distance from UUT connector u n to switching unit su a , and x, y and z are the three dimensional coordinates.
[0044] Once all connectors are assigned to their nearest SU, each SU is moved to its respective centroid 9 , 10 , 11 , or geographic center, of the group of UUT connectors assigned to it as shown in FIG. 3 . The X-Y-Z coordinates of the centroid is determined by the formula:
[0000]
X
C
=
∑
u
=
1
n
x
u
n
Y
C
=
∑
u
=
1
n
y
u
n
Z
C
=
∑
u
=
1
n
z
u
n
[0000] Where c is the centroid of a cluster of UUT connectors u 1 through u n . While the formula used in this embodiment equally weights each connector in the cluster, it is understood that other embodiments may assign weighted values to connectors based on the number of contacts within the connectors.
[0045] After the SUs are moved to the centroid of their respective connector clusters, the algorithm is repeated recursively. As shown in FIG. 3 , various connectors may be reassigned to another SU. For example, connector 5 was assigned to one SU 2 in the first pass, but is now nearer to another SU 1 . Because the total number of connectors in even the most complex UUT is small compared to the typical number of nodes analyzed by typical applications of K-means clustering, the algorithm processes each pass relatively quickly. Thus, a summary of the results of each pass of the algorithm may be presented, allowing the user to determine when enough passes have been performed in order to stop the process as shown in FIG. 4 . The determination to stop the process may also be automatic based on a set number of iterations or objective criteria (i.e., the fulfillment of a condition). For example, a process may automatically continue until the distance from the current location of any SU to the centroid of its cluster of connectors does not exceed a minimal value. In any case, once the SUs are assigned to an acceptable position, a position map can be generated. The position map specifies the position of each SU within the fuselage relative to the UUT connectors. For example, the position map can be a visual representation of the location of the SUs throughout the fuselage, or it can be a data set representing the location of the SUs. The position map can be generated in an output module, for example. One embodiment of a method according to the previous description is shown in a flow chart in FIG. 7 .
[0046] FIG. 5 illustrates that a typical UUT 12 may contain passenger floors 13 , aircraft skin 14 , and other physical barriers that block cables from connecting the UUT connectors 15 on one side of the barrier 13 to any SUs 16 on the opposite side of the barrier 13 . The user may input the physical locations of barriers 13 , 14 and may not include connectors on one side in the cluster associated with a SU on the opposite side. Given a simple barrier, such as barrier 13 (a floor), if the Y coordinate of an item 15 is greater than the Y coordinate of the barrier 13 , then the item is above the barrier 13 . If the Y coordinate of the item 16 is less than the Y coordinate of the barrier 13 then the item is below the barrier 13 . There are four possible combinations of UUT connector 15 location and SU 16 location relative to such a barrier: 1) both below the floor; 2) the connector above the floor and the SU below the floor; 3) the connector below the floor and the SU above the floor and; 4) both above the floor.
[0047] In this particular embodiment, rather than making multiple comparisons of the Y coordinates to quickly determine if a specific UUT connector 15 is on the same side of the barrier 13 as a SU, the following simple formula is tested to be true:
[0000] (( Y u −Y b )*( Y su −Y b ))≧0
[0000] where Y u is the Y coordinate of the UUT connector, Y b is the Y coordinate of the barrier (such as the passenger floor) and Y su is the Y coordinate of the test system switching unit. If false, then the connector and the switching unit are on opposite sides of the floor. The formula represents a specific instance of the general case where a coordinate on one side of a barrier results in a negative number while a coordinate on the opposite side of the barrier results in a positive number. By multiplying the results of two such coordinate differentials together, if they are both on the same side of the barrier, the product will be positive; if they are on opposite sides, the product will be negative. By extension it can be seen that any complex barrier topology can be accommodated by simply replacing the subtractions in the formula with a more complex test of the locations relative to a barrier, where the mathematical sign (plus or minus) of the result indicates whether the two items are on the same or opposite sides of the barrier.
[0048] FIG. 6 illustrates the test adapter connectors of a typical switching unit 18 according to an embodiment of the present invention. In one embodiment, the SU provides eight ITT Cannon DL1-156 connectors 17 . Each connector contains 156 contacts, 150 of which are connected to test switching for a total of 1200 test contacts in the complete unit. In such a case, if more than 1200 connections are assigned to the SU, then UUT connectors are reassigned to next nearest SU until the capacity of the current SU is no longer exceeded.
[0049] Embodiments of the invention also allow for a utilization factor to be included such that, for example, no more than 95% of the total physical capacity of the SU is utilized.
[0050] Although it is possible to manufacture a TAC cable that connects a single UUT connector across two or more SU connectors 17 , this is not a desirable configuration. Therefore, where practical, the capacity of a single SU output connector 17 , should not be exceeded. Thus, the algorithm is applied to the subset of UUT connectors assigned to each SU with the number of clusters being the number of SU test adapter connectors 17 . In this way, the UUT connectors are assigned to the specific SU adapter connectors and the capacity of each adapter connector is not exceeded.
[0051] In one embodiment, the final distances between UUT connectors and SUs is calculated as the taxicab distance in order to better represent the physical constraints of routing electrical cables across floors and vertically rather than creating an inaccessible array of cables routed in all directions. This also allows for additional cable length that may be necessary to route around physical obstacles that might appear in the test environment.
[0052] Other embodiments of the present invention may include:
[0053] a method/system for calculating the placement of test equipment hardware in and/or around a unit under test (UUT), the use of element clustering algorithms, such as K-means, to assign specific nodes, or points to be tested, to the tester units;
[0054] a method/system wherein the lengths of the test adapter cables connecting the nodes of the UUT to be tested to the tester units are calculated based on taxicab distances rather than line of sight;
[0055] a method/system wherein the nodes which have the least impact on the total TAC cable length are reassigned to alternate tester units if the initial clustering algorithm assigns a greater number of nodes than the capacity of the first tester unit;
[0056] a method/system wherein physical barriers to making connections, such as floors, walls, bulkheads, etc., are data modeled and said data models are used to prevent the routing of test adapter cables through said barriers;
[0057] a method/system wherein a single test case is used to determine if the barrier impacts the routing between the UUT node and the tester unit through testing mathematical sign of the product of the difference between the barrier coordinates and the UUT node and tester unit coordinates;
[0058] a method/system wherein the assignment of UUT connectors to the test adapter connectors on the individual tester units is based on clustering techniques as used to assign the UUT connectors to the tester units as a whole; or
[0059] a method/system wherein the representation of the assignments are either by tables of data or by tables of data augmented by a graphical representation of the UUT connector and SU locations.
[0060] It is understood that embodiments presented herein are meant to be exemplary. Embodiments of the present invention can comprise any combination of compatible features shown in the various figures, and these embodiments should not be limited to those expressly illustrated and discussed. Although the present invention has been described in detail with reference to certain configurations thereof, other versions are possible. Therefore, the spirit and scope of the invention should not be limited to the versions described above.
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Methods and systems for distributing equipment and adapters for electrical harness testing. Embodiments of the present invention provide a computer aided design (CAD) automated method of arranging test equipment elements and determining test adapter cable lengths based on the physical locations of the test nodes in the unit under test. Using these methods/systems, test setups may be quickly evaluated.
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BACKGROUND OF THE INVENTION
The present invention relates in general to a secondary air supply system which is constructed to supply air into an exhaust conduit system of an internal combustion engine for completely burning the remaining unburned combustible compounds, such as hydrocarbons (HC) and carbon monoxide (CO), contained in the exhaust gases emitted from the engine, and more particularly to a so called reed valve device which is employed in the secondary air supply system for promoting the admission of air into the exhaust conduit system of the engine by the pulsations of the exhaust gases passing through the conduit system.
In a reed valve device employed in the secondary air supply system, it is very necessary not only to minimize the air-flow resistance of the device for increasing the flow rate of air into the exhaust conduit system but also to tightly seal the device for completely preventing exhaust gas leaks into the open air. Furthermore, it is necessary to avoid the unpleasant chattering phenomenon caused by vibrations of the reed proper of the device.
In a conventional reed valve device, however, it has been observed that the connection of the reed valve device to its casing is made in such manner that a base on which the reed proper is mounted is directly connected to the casing by means of bolts. In this connecting method, there exists a possibility of warping of the base of the device as the bolts are screwed for connecting the same to the casing. This warping will cause the above-mentioned leaks of the heated exhaust gases into the open air. Furthermore, under this connecting condition, there will also occur a problem that the vibrations of the reed proper are directly transmitted to the casing of the reed valve device through the bolts thus causing the unpleasant noises.
SUMMARY OF THE INVENTION
Therefore, the present invention is proposed to eliminate the above-mentioned drawbacks encountered in the prior art reed valve device used in the secondary air supply system for the exhaust conduit system of the internal combustion engine.
It is an object of the present invention to provide a secondary air supply system having an improved reed valve device which is held in an air inlet section of the secondary air supply system only by means of a cushion member.
It is another object of the present invention to provide a secondary air supply system for admitting air into the exhaust conduit system of an internal combustion engine, the system comprising: a casing having one open end fluidly connected to the exhaust conduit system and the other open end communicates with the open air; non-return valve means disposed in the casing for temporally providing a fluid communication between the exhaust conduit system and open air when a negative pressure higher than the predetermined value is applied thereto from the exhaust conduit system; and an elastic frame member sealingly and tightly inserted between a clearance defined between the outer periphery of the non-return valve means and the inner surface of the casing.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and advantages of the secondary air supply system according to the present invention will become more clear from the following description when taken in conjunction with the accompanied drawings, in which:
FIG. 1 is a sectional view of a secondary air supply system according to the present invention, the system being illustrated to employ an improved reed valve device in an air inlet section thereof;
FIG. 2 is a plan view, partly cutaway to show the interior construction of the improved reed valve device;
FIG. 3 is a plan view of the reed valve device excluding some parts; and
FIG. 4 is a sectional view, partly cut away, taken along the line I-I of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 of the drawings, there is shown an air inlet section 10 of a secondary air supply system for an exhaust system of an internal combustion engine 12. The engine is illustrated to have a combustion chamber 14, a piston 16, a spark-plug 18, an exhaust valve 20 and an exhaust outlet 22 as is well known in the art. Furthermore, the engine 12 is formed with a passage 24 providing a fluid communication between an exhaust outlet 22 and an air injection manifold 26 mounted on the engine 12. The air injection manifold 26 communicates with the above-mentioned air inlet section 10 of the secondary air supply system through a conduit designated by the numeral 28.
The air inlet section 10 is mounted on an air filter casing 30 containing in it a pleated filter element 32 and having an opening 34. The filter element 32 is used for cleaning the air admitted into the internal combustion engine 12. The air inlet section 10 comprises a support member 36 which has a flat portion 36a with a hole 38, and a side wall portion 36b firmly connected at its lower end to the air filter casing 30 so as to surround the opening 34. Mounted onto the flat portion 36a of the support member 36 is a filter casing 40 which has also a flat portion 40a with a hole 42, and a side wall portion 40b firmly connected at its lower end to the flat portion 36a of the support member 36 by means of bolts and nuts 44. As shown, the filter casing 40 contains therein a filter element 46 which is sealingly sandwiched by two sealing members 48 adhered to the inner surfaces of the side wall portion 40b of the filter casing 40. With this construction, the space surrounded by the filter element 46, the support member 36 and the air filter casing 30 will act as an expansion chamber. Mounted on the flat portion 40a of the filter casing 40, by means of bolts and nuts 50, is a tube connector 52 which is formed at its one end with a reed valve device receiving portion 52a in the vicinity of the filter casing 40, the reed valve device receiving portion 52a having a generally rectangular cross section in this embodiment for the reason which will be described hereinlater. The tube connector 52 is further formed at the other end thereof with a tube connecting portion 52b connected with the prior mentioned conduit 28. Within the reed valve device receiving portion 52a of the tube connector 52 is disposed a reed valve device 54 which has an improved construction in comparison with the prior art device.
The reed valve device 54 comprises a generally rectangular shaped base member 56 which is tightly coupled in the prior mentioned reed valve device receiving portion 52a of the tube connector 52, through a sealing frame 58 made of some suitable elastomeric material such as rubber. The base member 56 may be constructed of aluminum alloy. As well shown in FIGS. 2 and 3, the sealing frame 58 is constructed to embrace the whole side edge of the base member 56. Preferably, the embracement by the frame 58 of the base member 56 is made in such a manner that, as well shown in FIG. 4, a recess 60 formed along an inner side of the frame 58 snugly receives therein a raised portion 62 which is provided along the outer side edge portions of the base member 56 for achieving a tight connection between the sealing frame 58 and the base member 56. The base member 56 is formed therein with two generally oval openings 64 which are equal in shape in this case. Around the openings 64 in the upper side of the base member 56 is formed a rectangular recess (no numeral) which receives therein a valve seat 66 made of some suitable elastomeric material such as rubber. Two reeds proper 68 each having a sufficient surface to cover up the corresponding opening 64 are connected at one end thereof to one side of the base member 56 through bolts 70. Preferably, each of the reeds proper 68 is made of stainless steel having a thickness ranging from 0.05 to 0.3 mm. A stopper 72 having two outwardly curved stopping arms 74 is fixed to the one side of the base member 56, by means of the bolts 70, for preventing the excess outward movement of the reeds proper 68 during the air inlet operation of the secondary air supply system.
Under the engine operation, pulsating negative pressure is generated in the exhaust conduit system including the exhaust outlet 22 and the passage 24 of the engine 12, so that air is intermittently fed into the exhaust conduit system by the pumping operation of the reed valve device 54. Now, it should be noted from the above, that the secondary air supply system including the above mentioned improved reed valve device 54 has the following advantages and merits, in which:
1. Since the connection of the reed valve device 54 to the reed valve device receiving portion 52a of the tube connector 52 is made only by the sealing frame made of elastomeric material, no deformation of the device 54, specifically of the base member 56, can occure so that preferable contacting surfaces between the reeds proper 68 and the valve seat 66 are formed. Thus, the leakage of the exhaust gases into the air filter casing 30 will be prevented. Furthermore, the vibrations of the reeds proper 68 due to the pulsation of the exhaust gases are not directly transmitted to the tube connector 52 connected to the air filter casing 30 which acts as a resonance box. Thus, generation of unpleasant noises due to the vibrations of the reeds proper 68 is repressed. Furthermore, the vibrations of the air filter casing 30 caused by the vibrations of the engine are not directly transmitted to the base member 56 with the reeds proper 68, so that the life-time of the reed valve device 54 is considerably extended. 2. Since the space surrounded by the filter elements 46, the support member 36 and the air filter casing 30 can act as an expansion chamber or a silencer, the unpleasant noises from the reeds proper will be decreased to a minimum.
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A reed valve device having two reeds capable of selectively closing and opening the corresponding openings formed in the device is snugly fitted in a casing through an elastomeric sealing member without using any other connecting means. The casing communicates with an exhaust conduit system of an internal combustion engine so that the reed valve device functions to intermittently admit air into the exhaust conduit system by the pulsations of the exhaust gas under pressure passing through the exhaust conduit system.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is related to a liquid crystal display device and method for driving the same, and more particularly, to a liquid crystal display device capable of reducing image flicker and method for driving the same.
2. Description of the Prior Art
Liquid crystals display (LCD) devices, characterized in low radiation, small size and low power consumption, have gradually replaced traditional cathode ray tube (CRT) devices and been widely used in electronic products, such as notebook computers, personal digital assistants (PDAs), flat panel TVs, or mobile phones. In traditional LCD devices, a source driver and a gate driver are used for driving the pixels of the panel in order to display images. Since the source driver is more expensive than the gate driver, LCD devices adopting half source driver (HSD) structure have been developed in order to reduce the number of source drivers. In other words, for the same amount of pixels, the manufacturing cost can be reduced by halving the number of data lines receiving signals from the source driver and doubling the number of gate lines receiving signals from the gate driver.
FIG. 1 is a prior art LCD device 100 which adopts HSD structure. The LCD device 100 includes a timing controller 130 , a source driver 110 , a gate driver 120 , a plurality of data lines DL 1 -DL m , a plurality of gate lines GL 1 -GL n , and a pixel matrix. The pixel matrix includes a plurality of pixel units PX L and PX R each having a thin film transistor (TFT) switch, a liquid crystal capacitor C LC and a storage capacitor C ST , and respectively coupled to a corresponding data line, a corresponding gate line and a common node. The timing controller 130 can generate control signals YOE and YV 1 C, input clock signals CK and CKB or an output enable signal OE for operating the source driver 110 and the gate driver 20 . The source driver 110 can generate data driving signals SD 1 -SD m corresponding to display images. If the gate driver 120 is an external driving circuit, the gate driving signals SG 1 -SG n for turning on the TFT switches are generated according to the control signals YOE and YV 1 C; if the gate driver 120 is fabricated using gate on array (GOA) technique, the gate driving signals SG 1 -SG n are generated according to the input clock signals CK,CKB and the output enable signal OE.
When the TFT switch is turned off, the pixel electrode is not connected to any voltage source and thus has a floating level. Any voltage variation around the pixel electrode is coupled to the pixel electrode via its parasite capacitance, which in turn influences the voltages applied to the liquid crystal capacitor C LC and the storage capacitor C ST . The feed-through voltage V FD due to voltage variations caused by parasite capacitance can be represented by the following equation:
V FD =[C GD /( C LC +C ST +C GD )]* ΔV G =K*ΔV G
C GD represents the parasite capacitance between the gate and the drain of the TFT switch. K represents the percentage of C GD which contributes to the overall parasite capacitance. ΔV G represents the gate voltage difference caused by a gate driving signal when turning off a corresponding TFT switch. The parasite capacitance is an inherent characteristic of the TFT switch. In order to effectively reduce image flicker, the gate voltage difference ΔV G needs to be lowered first before adjusting the common voltage Vcom for compensating the feed-through voltage V FD .
FIGS. 2 and 3 are diagrams illustrating methods for driving the prior art LCD device 100 . FIG. 2 shows the waveforms of the control signal YOE and the gate driving signals SG 1 -SG 4 when the gate driver 120 is an external circuit. FIG. 3 shows the waveforms of the clock signals CK, CKB, O_CK, O_CKB, the output enable signal OE and the gate driving signals SG 1 -SG 4 when the gate driver 120 is fabricated using GOA technique.
In the driving method depicted in FIG. 2 , the length of the enable period in the gate driving signals SG 1 -SG 4 is determined by the pulse width of the control signal YOE, and the length of the signal falling time in the gate driving signals SG 1 -SG 4 is determined by the signal falling start point of the control signals YOE and YV 1 C. In each period, the control signal YOE remains at high level for a constant length, and the waveform of the control signal YV 1 C starts to fall at the same point. Therefore, the gate driving signals SG 1 -SG 4 result in an identical gate voltage difference ΔV G ′ when turning off corresponding TFT switches. As previously stated, the feed-through voltage is proportional to the gate voltage difference. Since the gate voltage difference ΔV G ′ after voltage trimming is smaller than the gate voltage difference ΔV G without voltage trimming, the effect of the feed-through voltage can be compensated.
In the driving method depicted in FIG. 3 , the clock signals CK and CKB having opposite phases switch between high/low voltage levels based on a predetermined period which determines the length of the enable period in the gate driving signals SG 1 -SG 4 . When the output enable signal OE is at high level, the gate driver 120 outputs the clock signals CK and CKB for providing the corresponding clock signals O_CK and O_CKB. When the output enable signal OE is at low level, the gate driver 120 stops outputting the clock signals CK and CKB. Charge-sharing is then performed between the clock signals O_CK and O_CKB, thereby achieving voltage trimming at the signal falling edge. The gate driving signals SG 1 -SG 4 can thus be provided according to the clock signals O_CK and O_CKB after charge-sharing. In each period, the output enable signal OE remains at low level for a constant length T, the degree of voltage trimming in the gate driving signals SG 1 -SG 4 is identical. Therefore, the gate driving signals SG 1 -SG 4 result in an identical gate voltage difference ΔV G ′ when turning off corresponding TFT switches. As previously stated, the feed-through voltage is proportional to the gate voltage difference. Since the gate voltage difference ΔV G ′ after voltage trimming is smaller than the gate voltage difference ΔV G without voltage trimming, the effect of the feed-through voltage can be compensated.
In the prior art LCD device 100 , the pixel units are disposed on both sides of each data line, wherein the pixel units PX L disposed on the left side of the data lines are controlled by the gate driving signals SG 1 , SG 3 , . . . , SG n-1 transmitted from the odd-numbered gate lines, while the pixel units PX R disposed on the right side of the data lines are controlled by the gate driving signals SG 2 , SG 4 , . . . , SG n transmitted from the even-numbered gate lines. Normally adopting different designs, these two types of pixel units PX L and PX R have different C LC , C ST , C GS or C GD , and the value of the feed-through voltage V FD also varies. Even if the two types of pixel units PX L and PX R adopt the same design, the value of the feed-through voltage V FD may also vary due to characteristic shift caused by manufacturing process deviations, For example, the process shift between the first metal layer M 1 and the second metal layer M 2 may result in different C GD values of the pixel units PX L and PX R .
In the driving methods depicted in FIGS. 2 and 3 , the gate voltage difference of each pixel is lowered by the same degree. Since each pixel has different feed-through voltage, image flicker can not be effectively reduced by adjusting the common voltage Vcom.
SUMMARY OF THE INVENTION
The present invention provides an LCD device which improves image flicker, comprising a first gate line for transmitting a first gate driving signal; a second gate line adjacent and parallel to the first gate line for transmitting a second gate driving signal; a data line perpendicular to the first and second gate lines for transmitting data driving signals; a first pixel disposed at an intersection of the data line and the first gate line and on a first side of the data line, and for displaying images according to the first gate driving signal and a received data driving signal; a second pixel disposed at an intersection of the data line and the second gate line and on a second side of the data line, and for displaying images according to the second gate driving signal and a received data driving signal; a trimming circuit for generating a trimming signal according to the parasite capacitances of the first and second pixels; and a gate driver for generating the first and second gate driving signals by adjusting a signal falling edge of a gate pulse signal according to the trimming signal, wherein a signal falling edge of the first gate driving signal falls from a high level to a first level, and a signal falling edge of the second gate driving signal falls from the high level to a second level.
The present invention also provides a method for driving an LCD device which comprises a data line, two adjacent first and second gate lines, a first pixel disposed at an intersection of the data line and the first gate line and on a first side of the data line, and a second pixel disposed at an intersection of the data line and the second gate line and on a second side of the data line. The method comprises providing a gate pulse signal; generating a first gate driving signal by adjusting the gate pulse signal according to a parasite capacitance of the first pixel, wherein a signal falling edge of the first gate driving signal falls from a high level to a first level; generating a second gate driving signal by adjusting the gate pulse signal according to a parasite capacitance of the second pixel, wherein a signal falling edge of the second gate driving signal falls from the high level to a second level; and outputting the first and second gate driving signals to the first and second gate lines for driving the first and second pixels, respectively.
These and other objectives of the present invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram of a prior art LCD device which adopts HSD structure.
FIGS. 2 and 3 are diagrams illustrating methods for driving the prior art LCD device.
FIGS. 4 and 5 are diagrams of LCD devices which adopt HSD structure according to the present invention.
FIG. 6 is a timing diagram illustrating a method for driving the LCD device according to a first embodiment of the present invention.
FIG. 7 is a diagram illustrating the trimming circuit capable of performing the driving method according to the first embodiment of the present invention.
FIG. 8 is a timing diagram illustrating a method for driving the LCD device according to a second embodiment of the present invention.
FIG. 9 is a diagram illustrating the trimming circuit capable of performing the driving method according to the second embodiment of the present invention.
FIG. 10 is a timing diagram illustrating a method for driving the LCD device according to a third embodiment of the present invention.
DETAILED DESCRIPTION
FIGS. 4 and 5 are diagrams of LCD devices 200 and 300 which adopt HSD structure according to the present invention. The LCD devices 200 and 300 each include a source driver 210 , a gate driver 220 , a timing controller 230 , a trimming circuit 240 , a plurality of data lines DL 1 -DL m , a plurality of gate lines GL 1 -GL n , and a pixel matrix. The pixel matrix of the LCD device 200 includes a plurality of pixel units PX L and PX R , and the pixel matrix of the LCD device 300 includes a plurality of pixel units PX LU , PX LB , PX RU and PX RB . Each of the pixel units includes a TFT switch, a liquid crystal capacitor C LC and a storage capacitor C ST respectively coupled to a corresponding data line, a corresponding gate line and a common node. The timing controller 230 can generate control signals YOE and YV 1 C, clock signals CK and CKB or an output enable signal OE for operating the source driver 210 and the gate driver 220 . The source driver 210 can generate data driving signals SD 1 -SD m corresponding to display images. If the gate driver 220 is an external driving circuit, the trimming circuit 240 generates a trimming signal V TRIM according to the control signal YV 1 C and the parasite capacitance of the pixel units, and the gate driver 220 then generates the gate driving signals SG 1 -SG n for turning on the TFT switches according to the control signal YOE and the trimming signal V TRIM ; if the gate driver 220 is fabricated using GOA technique, the trimming circuit 240 generates a trimming signal V TRIM according to the output enable signal OE and the parasite capacitance of the pixel units, and the gate driver 220 then generates the gate driving signals SG 1 -SG n for turning on the TFT switches according to the clock signals CK, CKB and the trimming signal V TRIM .
In the LCD device 200 according to the present invention, the pixel units are disposed on both sides of each data line, wherein the first type of pixel units PX L disposed on the left side of the data lines are controlled by the gate driving signals SG 1 , SG 3 , . . . , SG n-1 transmitted from the odd-numbered gate lines, while the second type of pixel units PX R disposed on the right side of the data lines are controlled by the gate driving signals SG 2 , SG 4 , . . . , SG n transmitted from the even-numbered gate lines. Normally adopting different designs, these two types of pixel units PX L and PX R have different C LC , C ST , C GS or C GD /and the value of the feed-through voltage V FD also varies. Even if the two types of pixel units PX L and PX R adopt the same design, the value of the feed-through voltage V FD may also vary due to characteristic shift caused by manufacturing process deviations.
In the LCD device 300 according to the present invention, the pixel units are disposed on both sides of each data line, wherein the first type of pixel units PX LU disposed on the left side of the data lines are controlled by the gate driving signals SG 1 , SG 5 , . . . , SG n-3 transmitted from the gate lines GL 1 , GL 5 , . . . , GL n-3 , the second type of pixel units PX RB disposed on the right side of the data lines are controlled by the gate driving signals SG 2 , SG 6 , . . . , SG n-2 transmitted from the gate lines GL 2 , GL 6 , . . . , GL n-2 , the third type of pixel units PX RU disposed on the right side of the data lines are controlled by the gate driving signals SG 3 , SG 7 , . . . , SG n-1 transmitted from the gate lines GL 3 , GL 7 , . . . , GL n-1 , the fourth type of pixel units PX LB disposed on left side of the data lines are controlled by the gate driving signals SG 4 , SG 8 , . . . , SG n transmitted from the gate lines GL 4 , GL 8 , . . . , GL n (assuming n is a multiple of 4). Normally adopting different designs, these four types of pixel units PX LU , PX LB , PX RU and PX RB have different C LC , C ST , C GS or C GD /and the value of the feed-through voltage V FD also varies. Even if the four types of pixel units PX LU , PX LB , PX RU and PX RB adopt the same design, the value of the feed-through voltage V FD may also vary due to characteristic shift caused by manufacturing process deviations.
In the present invention, the gate driving signals SG 1 -SG n with trimmed signal falling edges are used for reducing the gate voltage differences. Meanwhile, the degree of voltage trimming is adjusted according to the parasite capacitance of the pixel units, so that the gate driving signals SG 1 -SG n result in various gate voltage differences ΔV G1 -ΔV Gn when turning off corresponding TFT switches. In the LCD device 300 for instance, the gate driving signals SG 1 -SG 4 with different trimmed signal falling edges are used for driving the four types of pixel units, thereby resulting in various gate voltage differences ΔV G1 -ΔV G4 when turning off corresponding TFT switches. The capacitance percentages K 1 -K 4 of the four types of the pixel units which influence the feed-through voltage differently can thus be compensated. Since the feed-through voltages V FD1 -ΔV FD4 of the four types of the pixel units are substantially the same after voltage trimming, image flicker can be effectively reduced.
FIG. 6 is a timing diagram illustrating a method for driving the LCD device 200 or 300 when the gate driver 310 is an external driving circuit according to a first embodiment of the present invention. FIG. 6 shows the waveforms of the control signal YOE and YV 1 C, the trimming signal V TRIM and the gate driving signals SG 1 -SG 4 . In the driving method depicted in FIG. 6 , the control signal YOE remains at high level for a constant length in each period, and the length of the enable period in the gate driving signals SG 1 -SG 4 is determined by the pulse width of the control signal YOE. The signal falling edge start points in each period of the control signal YV 1 C vary according to the parasite capacitances of the pixel units. The total lengths of the signal falling time T 1 -T 4 of the gate driving signals SG 1 -SG 4 are determined by the signal falling start points of the control signals YOE and YV 1 C in corresponding periods. The trimming circuit 340 first generates the trimming signal V TRIM having distinct signal falling edge start points in corresponding periods according to the control signal YV 1 C and the capacitance percentages K 1 -K 4 . The gate driver 320 then generates the gate driving signals SG 1 -SG 4 having distinct trimmed signal falling edges in corresponding periods according to the control signal YOE and the trimming signal V TRIM . The gate driving signals SG 1 -SG 4 result in different gate voltage differences ΔV G1 -ΔV G4 when the control signal YOE switches from high level to low level. Assuming the relationship of the capacitance percentages is K 1 <K 2 <K 3 <K 4 , then the relationship of the total lengths of the signal falling time is T 1 <T 2 <T 3 <T 4 , and the relationship of the gate voltage differences is thus ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . As previously stated, the feed-through voltage is proportional to the multiple of the capacitance percentage and the gate voltage difference. When K 1 <K 2 <K 3 <K 4 , the first embodiment of the present invention provides the gate driving signals SG 1 -SG 4 which result in gate voltage differences having the relationship of ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . Since the feed-through voltages of each type of pixel units are substantially the same after voltage trimming, image flicker can be effectively reduced by adjusting the common voltage Vcom.
FIG. 7 is a diagram illustrating the trimming circuit 340 capable of performing the driving method according to the first embodiment of the present invention. The trimming circuit 340 in FIG. 7 , including an inverter 70 , a level shifter 72 , a slope-adjusting circuit 74 , and transistor switches QP and QN, can generate the trimming signal V TRIM according to the control signal YV 1 C. When the control signal YV 1 C is at high level, the transistor switch QP is turned on and the transistor switch QN is turned off, and the trimming signal V TRIM is at a high level VGH. When the control signal YV 1 C is at low level, the transistor switch QP is turned off and the transistor switch QN is turned on, and the level of the trimming signal V TRIM is pulled down to low level via the resistor R 1 of the slope-adjusting circuit 74 . Therefore in the embodiments of FIGS. 6 and 7 , the trimming circuit 340 receives the control signal YV 1 C having distinct signal falling edge start points, and then provides the trimming signal V TRIM having a slope at the signal falling edge. The slope-adjusting circuit 74 can be an impedance device, such as a resistor or a variable resistor.
FIG. 8 is a timing diagram illustrating a method for driving the LCD device 200 or 300 when the gate driver 310 is an external driving circuit according to a second embodiment of the present invention. FIG. 8 shows the waveforms of the control signal YOE and YV 1 C, the trimming signal V TRIM and the gate driving signals SG 1 -SG 4 . In the driving method depicted in FIG. 8 , the control signal YOE remains at high level for a constant length in each period, and the length of the enable period in the gate driving signals SG 1 -SG 4 is determined by the pulse width of the control signal YOE. The signal falling edge start points in each period of the control signal YV 1 C vary according to the parasite capacitances of the pixel units. The waveform of the control signal YV 1 C starts to fall at the same point in each period, thereby resulting in an identical total length of the signal falling time T in the gate driving signals SG 1 -SG 4 . The slopes m 1 -m 4 of the signal falling edges in the gate driving signals SG 1 -SG 4 are determined by the trimming circuit 340 . The trimming circuit 340 first generates the trimming signal V TRIM having distinct signal falling edge slopes in corresponding periods according to the control signal YV 1 C and the capacitance percentages K 1 -K 4 . The gate driver 320 then generates the gate driving signals SG 1 -SG 4 having distinct trimmed signal falling edges in corresponding periods according to the control signal YOE and the trimming signal V TRIM . The gate driving signals SG 1 -SG 4 result in different gate voltage differences ΔV G1 -ΔV G4 when the control signal YOE switches from high level to low level. Assuming the relationship of the capacitance percentages is K 1 <K 2 <K 3 <K 4 , then the relationship of the signal falling edge slopes is m 1 <m 2 <m 3 <m 4 , and the relationship of the gate voltage differences is thus ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . As previously stated, the feed-through voltage is proportional to the multiple of the capacitance percentage and the gate voltage difference. When K 1 <K 2 <K 3 <K 4 , the second embodiment of the present invention provides the gate driving signals SG 1 -SG 4 which result in gate voltage differences having the relationship of ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . Since the feed-through voltages of each type of pixel units are substantially the same after voltage trimming, image flicker can be effectively reduced by adjusting the common voltage Vcom.
FIG. 9 is a diagram illustrating the trimming circuit 340 capable of performing the driving method according to the second embodiment of the present invention. The trimming circuit 340 in FIG. 9 , including an inverter 70 , a level shifter 72 , a slope-adjusting circuit 94 , and transistor switches QP and QN, can generate the trimming signal V TRIM according to the control signal YV 1 C. When the control signal YV 1 C is at high level, the transistor switch QP is turned on and the transistor switch QN is turned off, and the trimming signal V TRIM is at a high level VGH. When the control signal YV 1 C is at low level, the transistor switch QP is turned off and the transistor switch QN is turned on, and the level of the trimming signal V TRIM is pulled down to low level via the resistor R 1 of the slope-adjusting circuit 94 . The slope-adjusting circuit 94 , including a resistor R 1 , a variable resistor R 2 , and switches S 1 and S 2 , can provide different equivalent resistances according to the capacitance percentages K 1 *K 4 and can pull down the level of the trimming signal V TRIM using an adequate slope. Therefore in the embodiments of FIGS. 8 and 9 , the trimming circuit 340 receives the control signal YV 1 C having identical signal falling edge start points, and then provides the trimming signal V TRIM having distinct slopes at the signal falling edge using the slope-adjusting circuit 94 .
FIG. 10 is a timing diagram illustrating a method for driving the LCD device 200 or 300 when the gate driver 310 is fabricated using GOA technique according to a third embodiment of the present invention. FIG. 10 shows the waveforms of the clock signals CK, CKB, O_CK and O_CKB, the output enable signal OE and the gate driving signals SG 1 -SG 4 . In the driving method depicted in FIG. 8 , the clock signals CK and CKB having opposite phases switch between high/low voltage levels based on a predetermined period which determines the length of the enable period in the gate driving signals SG 1 -SG 4 . The trimming circuit 340 first generates a trimming signal OE TRIM having distinct disable lengths (low level) T 1 -T 4 in corresponding periods according to the enable signal OE and the capacitance percentages K 1 -K 4 . The gate driver 320 then outputs the clock signals CK and CKB for providing the clock signals O_CK and O_CKB. When the trimming signal OE TRIM is at high level, the gate driver 220 outputs the clock signals CK and CKB for providing the corresponding clock signals O_CK and O_CKB. When the trimming signal OE TRIM is at low level, the gate driver 220 stops outputting the clock signals CK and CKB. Charge-sharing is then performed between the clock signals O_CK and O_CKB, thereby achieving voltage trimming at the signal falling edge. The gate driver 320 then generates the gate driving signals SG 1 -SG 4 having distinct trimmed signal falling edges in corresponding periods according to the clock signals OCK and O_CKB.
The gate driving signals SG 1 -SG 4 result in different gate voltage differences ΔV G1 -ΔV G4 when the corresponding clock signals O_CK and O_CKB switch from high level to low level. Assuming the relationship of the capacitance percentages is K 1 <K 2 <K 3 <K 4 , then the relationship of the disable lengths is T 1 <T 2 <T 3 <T 4 , and the relationship of the gate voltage differences is thus ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . As previously stated, the feed-through voltage is proportional to the multiple of the capacitance percentage and the gate voltage difference. When K 1 <K 2 <K 3 <K 4 , the third embodiment of the present invention provides the gate driving signals SG 1 -SG 4 which result in gate voltage differences having the relationship of ΔV G1 >ΔV G2 >ΔV G3 >ΔV G4 . Since the feed-through voltages of each type of pixel units are substantially the same after voltage trimming, image flicker can be effectively reduced by adjusting the common voltage Vcom.
The present invention can adjust the total length or the slope of the signal falling edge in the gate driving signals SG 1 -SG 4 according to the capacitance percentages K 1 -K n of the pixel units. Different parasite capacitances can be compensated by various voltage differences ΔV G1 -ΔV Gn so that the feed-through voltages of each type of pixel units are substantially the same. The present invention can effectively reduce image flicker the by adjusting the common voltage Vcom, and thus provide better display quality.
Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention.
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A method for driving a liquid crystal display adjusts the falling edges of the gate driving signals for reducing image flicker. A first gate driving signal falls from a high level to a first level at the signal falling edge. A second gate driving signal falls from the high level to a second level at the signal falling edge. When the parasitic capacitance of a first pixel is larger than that of a second pixel, the first level is lower than the second level; when the parasitic capacitance of the first pixel is substantially the same as that of the second pixel, the first level is the same as the second level; when the parasitic capacitance of the first pixel is smaller than that of the second pixel, the first level is higher than the second level.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims subject matter disclosed in Provisional Patent Application Serial No. 60/403,494, filed Aug. 14, 2002.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention is in the field of piezoelectric transducers for ultrasound devices, more particularly, piezoelectric transducers comprising piezoelectric cylinders isolated from a support matrix by a gas or vacuum and arranged such that they are separated from each other by less than one wavelength in that matrix.
[0004] 2. Description of Related Art
[0005] Transducers are devices that transform input signals into output signals of a different form. In ultrasound devices, they transform signals of electrical energy into acoustic energy or produce electrical signals from absorbed sound waves. Piezoelectric ceramic materials are particularly effective for this type of electromechanical energy conversion and have found wide use in the transducer field. Many piezoelectric ceramics have very high electromechanical coupling coefficients, k T (approximately 0.5), which indicate how effective a material is at transferring electrical energy into mechanical energy.
[0006] In the fields of non-destructive testing of materials, biomedical non-invasive diagnostics, and ultrasonic power generation, it is highly desired that the source (transmitter) of ultrasound, that is, the transducer device, be characterized by high transduction in the medium of transmission. It is further desired that the receiver of ultrasound be very sensitive to detect even the minutest ultrasonic vibrations, irrespective of the medium or the mechanism by which they are generated.
[0007] A second important property for effective ultrasound transducers is the acoustic impedance of the transducer material. Acoustic impedance describes the compressibility of a material and is found by taking the product of the density of a material and the velocity of sound in that material. When a sound wave propagating in material X encounters an interface between X and a second material Y, the size of the difference between the acoustic impedances of X and Y determines the amount of sound energy that is transmitted across the interface and the amount of sound energy that is reflected back into the first material. The greater the difference, the less sound energy that is received into the second material. The transmission of sound energy between two materials is termed acoustic coupling, higher coupling means higher transmission of sound energy. The size of the difference between the values of acoustic impedance is what determines the degree of acoustic coupling in that system. Systems with low differences in acoustic impedance exhibit the best coupling. Piezoelectric ceramics, such as Pb(Zr, Ti)O 3 (PZT), have very high acoustic impedances (Z), on the order of 10 7 Rayl (kg/m 2 .*s), as compared with air, where Z=410 Rayl. In ultrasound applications, the large difference in acoustic impedance between the probe material (e.g., water) and the monolithic piece of ceramic results in a large proportion of reflected sound waves at the transducer surface. Therefore, the information contained in those sound waves about the probed material is lost because it is not received by the transducer efficiently.
[0008] One solution to this problem of poor acoustic coupling is to, create matching layers between the monolithic piece of ceramic and the sample and to use a backing medium behind the ceramic. These layers attenuate sound energy and still lose energy to reflection and are not a perfect solution to the problem. A second solution is to combine the strong piezoelectric characteristics of a ceramic with the better acoustic coupling properties of another material in a composite. Most early attempts to create composites involved loading ceramic particles into a polymer matrix to create a homogenous composite. These composites had low acoustic impedances, but the polymer shielded the piezoelectric ceramic particles from applied electric fields, preventing poling of the ceramic particles. In addition, the polymer acted to dampen waves generated by the ceramic.
[0009] Efforts to solve these problems resulted in the development of composites consisting of a porous three-dimensional piezoelectric ceramic network, which could be impregnated with a polymer to lower the acoustic impedance of the overall structure. Shrout et al. U.S. Pat. No. 4,330,593 discloses a method for forming a so-called 3-3 structure (3-3 indicates the ceramic is interconnected in all three directions, and the polymer is also interconnected in all three directions). Since their development, it has been realized that the nature of the phase interconnection controls the dielectric flux pattern and mechanical stress distribution in the composite material.
[0010] One theoretically promising arrangement of phases taught by Klicker et al. in U.S. Pat. No. 4,412,148 was a polymer matrix connected in three dimensions, impregnated with piezoelectric ceramic rods oriented in the same direction. This design was termed 1-3 connectivity. The theoretical concept was that the polymer matrix was much softer and had better acoustic coupling with water or tissue and would deform when impacted by a sound wave. The polymer would bind to the side surfaces of the piezoelectric ceramic rods and would transfer the strain energy into the ceramic. In this configuration, the many small rods would have a much greater surface area under strain than a monolithic ceramic. It was hoped this would result in more mechanical energy being transferred. While this configuration did not realize its theoretical potential, partially because most polymers used had very high Poisson ratios which generated internal stresses that opposed the applied stress of the sound waves, it was still a tremendous improvement over previous designs in terms of piezoelectric voltages and sensitivity. The lower dielectric permitivity of the polymer allowed for more complete poling of the piezoelectric material. More complete poling, coupled with a lower overall dielectric constant, allowed for higher piezoelectric voltages than in the monolithic ceramic.
[0011] While these composites offer improved acoustic coupling and mechanical response, they still have problems. Depending on the arrangement of rods in the matrix, there is the potential for a so-called grating lobe, a form of acoustic noise, to develop during transmission of ultrasonic waves. Grating lobes consist of undesirable ultrasonic waves being emitted in the directions determined by the pitch of the piezoelectric cylinder arrangement, which acts to deteriorate the ultrasound image. Nakaya et al. U.S. Pat. No. 4,658,176 offered a solution to this problem by spacing apart the cylinders at less than one wavelength of the fundamental frequency of the transducer. This arrangement was found to ameliorate the problem of grating lobe formation and improve ultrasound images obtainable with 1-3 composites.
[0012] Despite these improvements, performance problems still remain for piezoelectric transducers. The modern piezoelectric composites offer excellent acoustic matching for human tissue and the flexibility needed for medical probes, but they still have acoustic impedances which remain much greater than what is needed for non-contact applications where transmission through air is necessary. Non-contact ultrasound, which is particularly important for materials characterization, requires good acoustic coupling between air and the transducer to achieve high resolution and polymers with acoustic impedance values in excess of 10 6 Rayl.
[0013] An additional challenge in all piezoelectric ceramics is an effect known as planar coupling. In most transducers, the composite is placed between electrodes and polarized in the direction perpendicular to the electrodes, or the 3 direction. The object is to apply an electric field to the composite and cause displacement in the 3 direction, generating ultrasound waves. In most piezoelectric ceramics, such as PZT, when a field is applied in the 3 direction, there is simultaneous mechanical action in the 1 and 2 directions that are perpendicular to the 3 direction. This is known as planar coupling. While reducing the size of the piezoelectric element helps reduce the magnitude of the planar coupling, the problem remains. In 1-3 composites, planar coupling in the piezoelectric cylinders generates vibrations that propagate through the polymer to other elements in the transducer creating noise, which is termed crosstalk in the art. This noise reduces the resolution of the device. This type of noise is especially troublesome in devices where one part of the array of cylinders is used to transmit ultrasound waves and another part is used to receive the reflected waves. In these arrangements, the waves resulting from planar coupling in the transmitting cylinders are propagated through the polymer to the receiving cylinders creating noise and reduce the image quality. Therefore, the object of the present invention is to overcome deficiencies in the prior art.
[0014] The current ultrasonic transducer devices utilize a piezoelectric material, the front and back faces of which are bonded with a variety of materials that modify the resonance and frequency characteristics of the piezoelectric material with respect to ultrasound transmission in a given medium. In such devices, the piezoelectric materials used are: Lead Zirconate-Lead Titanate solid solutions, Lead meta Niobates, Lead Titanates, Lead Magnesium Niobate, Lithium Niobate, Zinc Oxide, Quartz, Barium Titanate, polymer-based homogeneous materials, polymer matrix solid piezoelectric materials, etc. Materials used on the back, front, and on the sides of the piezoelectric materials are: rigid, porous, monolithic or composite, particulate, or fibrous metals, alloys, ceramics, polymers, etc. Depending upon the type of piezoelectric material and those that surround it, the devices according to the current art can be made to generate high transduction in the medium of ultrasound transmission. See Bhardwaj U.S. Pat. No. 6,311,573.
[0015] If the devices according to the current art are to be used for certain applications, such as for power generation or for high transduction in attenuative media (gases, coarse grained, open or closed cell materials) particularly in high frequency range, say from 100 kHz to greater than 1 MHz, then one has to apply relatively high electrical power to the devices. Whereas some applications can be successfully executed by doing so, yet there are others that cannot. The reason for this being high power excitation of transducers results in the heating of the piezoelectric material, subsequently destroying the entire device. Besides this, too high electrical power can be dangerous and more cumbersome to handle in a practical manner. Therefore, it is necessary to develop a piezoelectric device that is inherently characterized by transduction efficiency higher than those that are produced according to the current art. The present invention has been shown to overcome the limitations of the prior art.
SUMMARY OF THE INVENTION
[0016] Briefly, according to this invention, there is provided a piezoelectric transducer defined by two faces. The transducer comprises a plurality of piezoelectric cylinders. The axial length and composition of the piezoelectric cylinders determine the frequency of the transducers when excited. The axial ends of the piezoelectric cylinders are aligned with the faces. The piezoelectric cylinders are separated from each other in a manner to substantially reduce or substantially eliminate crosstalk. The piezoelectric cylinders or fibers may be separated from each other by a space that is empty or a space that is partially empty of matrix material resulting in a gap between the cylinders and the material so that cylinders and material are substantially entirely unconnected. The piezoelectric cylinders are separated from each other by a distance that is preferably less than the acoustic wavelength at the frequency of the piezoelectric cylinders or fibers in the space between the cylinders. Electrodes are provided at the faces of the transducer for simultaneously exciting the piezoelectric cylinders.
[0017] According to another embodiment of this invention, a piezoelectric transducer is defined by two substantially parallel faces and a support structure provides mechanical strength to the transducer between the faces. Piezoelectric cylinders are arranged between the parallel faces with cylindrical axes substantially perpendicular to the parallel faces. The axial length and composition of the piezoelectric cylinders determine the frequency of the transducers when excited. The piezoelectric cylinders are separated from each other by a space and there is a gap in the space free of solid or liquid material. The piezoelectric cylinders are separated from each other by a distance that is preferably less than the acoustic wavelength at the frequency of the piezoelectric cylinders in the space therebetween. Electrodes are provided at the parallel faces of the transducer for simultaneously exciting the cylinders.
[0018] The piezoelectric cylinders may have one or more of the following cross sections: circular, rectangular, hexagonal, or any other polygon, with a width preferably less than one wavelength of the frequency in the piezoelectric material.
[0019] The material may comprise a solidified foam, fiber batting or honeycomb, for example, which material is not electrically conductive.
[0020] The gap in the space between the piezoelectric cylinders may be filled with a gas at atmospheric pressure, gas below atmospheric pressure, or a vacuum.
[0021] Other objects and features of the invention will appear in the course of the description thereof, which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] [0022]FIG. 1A is a schematic drawing of the perforated foam material, and FIG. 1B is a schematic drawing of a honeycomb core suitable as a support matrix;
[0023] [0023]FIGS. 2A and 2B are schematic drawings of a perforated foam material and a honeycomb core, respectively, supporting piezoelectric ceramic cylinders;
[0024] [0024]FIG. 3 is a drawing showing the relationship between the support matrix and the piezoelectric cylinders, preferably the width of the cylinder d1 and the distance between the cylinders d2 are less than one wavelength in the piezoelectric material at a specified frequency;
[0025] [0025]FIG. 4 is a section view of the transducer according to this invention with the surface fully electroded, the spacing between the cylinders and the width of the cylinders being less than one wavelength at a specified frequency, and t is the thickness of the transducer;
[0026] [0026]FIG. 5 is a section view of the transducer according to this invention with the alternative method of electroding individual cylinders rather than the entire surface for reduction of the penetration of conducting material into the support matrix, the spacing between the cylinders and the width of the cylinders being less than one wavelength at a specified frequency, and t is the thickness of the composite;
[0027] [0027]FIGS. 6A and 6B show a schematic drawing of an array with electrodes applied to rows of cylinders in two different ways;
[0028] [0028]FIG. 7 is a schematic illustration of an arrangement of equal length piezoelectric cylinders arranged for focusing;
[0029] [0029]FIG. 8 is a schematic illustration of an arrangement of piezoelectric cylinders of variable lengths to produce a broadband transducer;
[0030] [0030]FIG. 9 is a schematic cross-sectional view through a transducer assembly according to this invention;
[0031] [0031]FIG. 10 is an oscilloscope trace showing a signal reflected through air from a surface to a comparative polymer matrix transducer;
[0032] [0032]FIG. 11 is an oscilloscope trace showing a signal reflected through air from a surface to a gas matrix transducer made according to this invention;
[0033] [0033]FIG. 12 is an oscilloscope display showing a reflected signal through air from a surface to a polymer matrix transducer with the top trace being the entire signal and the bottom trace the amplified reflected signal;
[0034] [0034]FIG. 13 is an oscilloscope display showing a reflected signal through air from a surface to a gas matrix transducer according to this invention with the top trace being the entire signal and the bottom trace the amplified reflected signal;
[0035] [0035]FIG. 14 is an oscilloscope display showing the crosstalk between two gas matrix transducers according to this invention in physical contact with each other;
[0036] [0036]FIG. 15 is an oscilloscope display showing the crosstalk between two comparative polymer matrix transducers in physical contact with each other;
[0037] [0037]FIG. 16 is an oscilloscope display showing fully resolved multiple reflected signals through air from a surface to a gas matrix transducer according to this invention;
[0038] [0038]FIG. 17 is an oscilloscope display showing poorly resolved multiple reflected signals through air to a comparative polymer matrix transducer;
[0039] [0039]FIG. 18 is a schematic cross section of an array of transducers according to one embodiment of this invention;
[0040] [0040]FIG. 19 is a schematic plan view of a linear array of transducers according to this invention; and
[0041] [0041]FIG. 20 is a schematic plan view of a two-dimensional array according to this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0042] The transducer of the present invention uses piezoelectric cylinders with a preferred diameter of less than one wavelength of the frequency in the piezoelectric ceramic. These cylinders are preferably set apart by a distance less than one wavelength of the frequency in the support matrix. The support matrix may consist of foams, ceramics, polymers, fiber batting, or other materials that allow for voids into which the piezoelectric cylinders may be inserted. The piezoelectric cylinders are separated, except for incidental brushing contact, from the matrix material by a layer of gas or a vacuum, isolating the piezoelectric elements from the support matrix.
[0043] This invention improves on the prior art performance of these arrays of piezoelectric cylinders, which are normally embedded and bonded to some type of polymer matrix, by isolating them in a support matrix which provides mechanical strength of the overall transducer assembly and protects the array of piezoelectric cylinders. In previous designs, the deformation of the matrix along with the piezoelectric elements was the essential feature of the composite's operation. The current design instead focuses on mechanically isolating the piezoelectric elements to prevent electromechanical crosstalk between adjacent cylinders. This isolation also serves to reduce the effects of planar coupling on resolution and sensitivity. The composite still benefits from the lowered overall dielectric constant, which allows high voltages to be obtained when ultrasound waves are received as compared to a monolithic piezoelectric ceramic. The design also lowers the overall transducer acoustic impedance allowing for better coupling between the transducer and air or other low impedance materials.
[0044] The transducer of the current design may be constructed by taking a support matrix, such as a foam with holes drilled in it (as shown in FIG. 1A) or a honeycomb structure (FIG. 1B), and inserting a piezoelectric ceramic (e.g., LiNbO 3 , Pb(Zr, Ti)O 3 , Pb,Mg(NbO3), Pb(Zr, Ln, Ti)O 3 ) cylinders into the holes (as shown in FIG. 2A) or cells of a honeycomb structure (FIG. 2B). The width of the cylinder preferably should be less than one wavelength of a specified frequency in the piezoelectric material. The holes or cells in the support matrix material must be spaced such that the distance between them is preferably less than one wavelength in the matrix material. The reason for the width and spacing in the transducer is to reduce or eliminate the problems with acoustic nodes.
[0045] [0045]FIG. 3 illustrates the relationship between the matrix and the piezoelectric cylinders. The diameter d1 of the cylinders is preferably less than one wavelength of the piezoelectric material. The spacing d2 between adjacent piezoelectric cylinders is less than one wavelength of the matrix gas and structure at the frequency of the transducer.
[0046] [0046]FIG. 4 illustrates a common electrode sheet for exciting all piezoelectric cylinders at one time. FIG. 5 illustrates lead wires to each individual piezoelectric cylinder. The latter arrangement, while more difficult to fabricate, will be less susceptible to crosstalk between cylinders. FIGS. 6A and 6B illustrate alternate arrangements for attaching strips of conductive material across the ends of the piezoelectric cylinders.
[0047] Metallic and non-metallic honeycomb materials are commercially available, for example, from Hexal Composites, Duxford, Cambridge CB2 4QD, United Kingdom. These honeycomb materials have thin walls comprised of various materials, such as glass fabric reinforced with phenolic resin and paper reinforced with phenolic resin. The walls divide off the cells, which may have a hexagonal cross section. One suitable honeycomb structure is formed of abutting corrugated layers wherein the peaks of one layer are attached to the grooves of the other layer. There are many ways of making honeycomb structures. See, for example, Dixon et al. U.S. Pat. No. 5,571,369.
[0048] The piezoelectric cylinders are not attached to the support matrix material, though there can be some contact between the support matrix and the cylinders. A key feature is that the gaps between the cylinders and the support matrix are filled with some gas, mixture of gases, or a vacuum. While the prior art has relied on surface contact and attachment between the cylinders and the matrix material to transfer energy between the matrix and the ceramic, the current invention makes use of this gap to isolate the cylinders minimizing mechanical crosstalk and noise between the piezoelectric elements. The gas or vacuum between the support matrix and the rods allows for improved coupling with air in non-contact applications, while still being able to take advantage of the larger piezoelectric voltages and improved sensitivity offered by the piezoelectric cylinders in a 1-3 arrangement over a monolithic ceramic.
[0049] In the prior art, the focus was on the matrix properties and finding a matrix arrangement that would optimize overall composite properties, such as dielectric constant or acoustic impedance. In the present invention, the focus is on the piezoelectric elements, their arrangement, and isolation to optimize their performance. In a transducer making use of the current invention, improved performance is realized by combining ceramic element size and shape, which effectively eliminates planar coupling coefficients and raises piezoelectric voltages in the overall transducer arrangement, with the benefits of mechanical isolation, such as reduced noise and crosstalk between elements in the transducer. The support matrix used in one embodiment of the current invention serves primarily to impart mechanical strength or flexibility to the piezoelectric array.
[0050] In some applications, better performance may be realized by taking the isolation a step further by removing the support matrix material entirely and leaving only gas or vacuum between the piezoelectric cylinders. This configuration would take advantage of the complete mechanical isolation of the piezoelectric cylinders to provide for better resolution of the reflected ultrasound waves. When no support matrix is used, the cylinders may be held in place by placing them between two horizontal metal plates and bonding the plates to the top and bottom faces of the cylinders.
[0051] The other important feature is the electroding on the surface of the composite, which provides electrical connection to the control and measuring devices. The electroding can either be on the full surface of the composite or the individual faces of the piezoelectric cylinders. When the surface is fully electroded, care must be taken to prevent the conductive material (Cu, Al, Au, Ag, Ni, Pt, etc.) from penetrating into the matrix material.
[0052] Gas matrix piezoelectric material is characterized by the following highly desired characteristics: extremely high thickness mode coupling, which is equal to that of the solid piezoelectric material; practically zero planar coupling, which is usually very high for high coupling piezoelectric materials; very low dielectric constant; very low density; and very low pyroelectric charge development.
[0053] [0053]FIG. 7 shows the cross section of equal length piezoelectric cylinders arranged between two faces that are curved in order to generate a geometric focus. The type of curvature can be spherical to produce a point focus, it can be parabolic to create a cylindrical focus, or it can be a combination of the two to create a compound focus.
[0054] [0054]FIG. 8 shows the cross section of variable length piezoelectric cylinders arranged between a plane face and a curved face. By doing so, the axial length of the solid piezoelectric cylinders and correspondingly that of the matrix will be different at different places, the magnitude of which is defined by the radius of curvature of the curved face. In this embodiment, it is preferred that the thickness T2 of the central portion of the material be one half of that of the outermost thickness T1. By do so, it is possible to make a very broadband gas matrix piezoelectric material, because it is characterized by multiple frequencies within the thickness T1 and T2 of the solid piezoelectric material.
[0055] [0055]FIG. 9 shows the details of a transducer device based upon gas matrix piezoelectric materials. The gas matrix piezoelectric material 1 has a frequency which is determined by the formula: F=FC/t, where FC is the frequency constant (mm*MHz) and t is the thickness of the gas matrix composite in millimeters. The composition of acoustic impedance or Z matching single or multiple layers 2 abutting the piezoelectric materials have a composition that determines the efficiency of ultrasound transmission in the medium in which propagation of ultrasound is desired. The total thickness of this layer, individually or collectively (if multiple), preferably should be one-quarter of the wavelength in the Z matching layer. The thickness d of the Z matching layer in mm is determined by the formula: d=λ/F, where λ is the wavelength in the acoustic impedance matching layer in millimeters, and λ=V/F, where V is the velocity of ultrasound in the Z matching layer. The Z matching layer materials may comprise single or multiple layers of homogeneous or particulate or fibrous metals, ceramics, polymers, or their combinations.
[0056] Depending upon the physical characteristics of the damping material 3 , this material modifies the pulse shape and the frequency characteristics of the ultrasound device. The thickness of this material is less than one-eighth of the wavelength or more, preferably, one quarter of the wavelength. The damping materials may comprise single or multiple layers of homogeneous or particulate or fibrous metals, ceramics, polymers, or their combinations. Electrically conductive wires 4 are bonded to the faces of the piezoelectric material and to a suitable coaxial cable or connector 8 . The transducer housing 5 may comprise metal, ceramic, polymer, or a composite. The sides 6 of the transducer may be encapsulated with a material, such as non-electrically conductive epoxy, rubber, or inorganic cement. If desired, an electrically tuning network 7 may be installed between the −ve and +ve faces of the piezoelectric composite.
[0057] A comparison between the polymer matrix and gas matrix piezoelectric transducers is informative. The testing was conducted at a frequency of about 125 kHz. The active area of the transducers was 50×50 mm. The transducers were excited with a 220 volt negative spike pulse. A steel plate was placed 180 mm away from the transducer in ambient air. The gain of the receiver was 20 dB. FIG. 10 is an oscilloscope display recording the reflected pulse for a polymer matrix transducer. The amplitude of the reflected pulse is 0.52 volts. FIG. 11 is an oscilloscope trace recording the reflected pulse for a gas matrix transducer according to this invention. The amplitude of the reflected pulse is 1.33 volts. Upon comparison of the polymer and gas matrix piezoelectric materials, it is apparent that the reflected signal of the latter is more than 60% or more than 8 dB greater than that of the former. Similar improvement is observed when the devices made for operation in water and in contact with solid materials are tested.
[0058] A further comparison of polymer matrix piezoelectric and gas matrix piezoelectric transducers in ambient air was made as follows: Frequency: 100 kHz. Active area: 50×50 mm. Excitation: 220 V negative spike. Relative gain: 20 dB. Reference signal: Reflection from a flat steel plate about 180 mm away from the transducer in ambient air. FIGS. 12 and 13 are oscilloscope displays showing the excitation pulse and reflected signals for the polymer matrix and gas matrix transducers, respectively. The top trace is the complete signal and in the bottom trace the horizontal scale has been changed to show the details of the signal reflected from the steel plate at 180 mm away from the transducer in ambient air.
[0059] [0059]FIG. 12 shows that the polymer matrix piezoelectric transducer had a low signal-to-noise ratio and a definitely noisy time base. The reflected signal amplitude was 0.5 volts. FIG. 13 shows that the gas matrix piezoelectric transducer has a very high signal-to-noise ratio and a very clean time base. The reflected signal amplitude was 1 volt which is 6 dB (50%) higher than the polymer matrix piezoelectric transducer. It should be noted that the conditions of transducer excitation and signal amplification in FIGS. 12 and 13 are the same. By comparison, the gas matrix piezoelectric transducer according to this invention is excellent. The improved signal-to-noise ratio is due to the substantial elimination of the radial component of the piezoelectric materials. A further benefit of the substantial elimination of the radial components is that adjacent transducers do not transfer radial components.
[0060] If an application demands more than one transducer to be placed side-by-side, such as in the case of linear, phased, or matrix arrays, then the gas matrix based piezoelectric transducers offer a significant advantage. This advantage pertains to the fact that gas matrix piezoelectric material is virtually free from the deleterious effects of planar coupling. Therefore, multiple transducers based upon this invention can be closely placed against each other without practically any crosstalk between them. FIGS. 14 and 15 illustrate the crosstalk between two abutting gas matrix transducers and two adjacent polymer matrix transducers, respectively. FIGS. 16 and 17 illustrate relative signal-to-noise ratio of multiple reflections from a flat target at 60 mm. The reflected signal for the gas matrix transducer is fully resolved upon receipt of the first reflection. The noise prevents full resolution until a much later time.
[0061] The extremely low crosstalk between adjacent transducers according to this invention makes possible linear and two-dimensional arrays of the transducers.
[0062] [0062]FIGS. 18 and 19 show the schematics of a linear array. FIG. 20 shows the schematics of a matrix array. Individual transducers in the array design can be of any desired shape. With two-dimensional arrays, instant sonic pictures are possible.
[0063] Gas matrix piezoelectrics are lighter by more than 50% relative to polymer based piezoelectric composites and more than lighter relative to solid piezoelectric materials, have higher resolution, have zero crosstalk, and can have complex shapes. Pyroelectric effects are much lower, therefore, much lower surface temperatures of transducers, therefore, easier to handle, have longer life, and are more robust.
[0064] Having thus described my invention with the detail and particularity required by the Patent Laws, what is desired protected by Letters Patent is set forth in the following claims.
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A piezoelectric transducer defined by two faces comprises a plurality of piezoelectric cylinders. The axial length and composition of the piezoelectric cylinders determines the frequency of the transducer when excited. The axial ends of the piezoelectric cylinders are aligned with the faces. The piezoelectric cylinders are separated from each other and the space therebetween is fully or partially empty such that crosstalk between piezoelectric cylinders is substantially eliminated.. Electrodes are produced at the faces of the transducer for simultaneously exciting the piezoelectric cylinders.
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FIELD OF THE INVENTION
[0001] The present invention relates to a load balancer and more particularly to a pneumatically operated load balancing hoist.
DESCRIPTION OF THE PRIOR ART
[0002] Fluid operated hoists which include means for balancing the load while the load is being raised, lowered, or moved from one position to another have been in use for a number of years. Such hoists are in common use for supporting loads such as workpieces or tools that have to be positioned relative to a work operation where the loads are too heavy to be conveniently manipulated by hand at all or for any extended period of time.
[0003] An early example of such a load balancing hoist can be found in U.S. Pat. No. 2,500,879 to C. D. P. Smallpiece. That patent illustrates a pneumatically operated hoist in which balancing is achieved by moving a piston within a housing to move a pulley through a piston rod to raise and lower a hoisting cable. A manually operated control valve regulates the pressure applied to the piston to achieve the balancing effect for the hoist as the workload is manipulated.
[0004] U.S. Pat. Nos. 3,669,411 and 3,675,899 both issued to McKendrick disclose balancers similar in construction to the Smallpiece patent. These patents are directed to the control circuit for controlling operation of the balancer.
SUMMARY OF THE INVENTION
[0005] The present invention provides a load balancing hoist that is substantially less costly to produce than load balancing hoist of the prior art. Such prior art hoists are commonly constructed as shown in FIG. 1 accompanying this description and include a power module having as a part thereof a pneumatically actuated piston and piston rod assembly which moves a moveable pulley in a travel module toward and away from a fixed pulley to raise and lower the cable carrying a load. The distance the travel module is permitted to move determines the length that the cable can be extended from the hoist.
[0006] As will be apparent as the description of the balancing hoist of the present invention proceeds the power module and the travel module of prior art devices has been combined into a single unit. The piston rod of the prior art construction has been eliminated and the result is a compact load balancing hoist that is less costly to produce than those of the prior art without sacrifice to its operation or application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] A preferred embodiment of the improved load balancing hoist of the present invention is illustrated in the following drawings in which;
[0008] FIG. 1 is a longitudinal cross sectional view illustrating a load balancing hoist constructed in the manner shown in the prior art;
[0009] FIG. 2 is a longitudinal cross sectional view of a load balancing hoist of the present invention;
[0010] FIG. 3 is a transverse cross sectional view of the hoist shown in FIG. 2 taken substantially at line 3 - 3 of FIG. 2 ; and
[0011] FIG. 4 is a transverse cross sectional view similar to FIG. 3 but taken substantially along line 4 - 4 of FIG. 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0012] FIG. 1 illustrates a load balancing hoist constructed in accordance with the prior art. The hoist 10 shown in FIG. 1 is constructed substantially like the hoist shown in U.S. Pat. No. 3,669,411. A cable 12 extends from the hoist 10 to support a load (not shown) at the end of the cable 12 .
[0013] The hoist 10 includes a housing 14 having one end closed by a front end cap 16 and the other end closed by a rear cap 18 to define a cylindrical chamber 18 . A dual piston assembly 20 is supported for movement axially within the chamber 18 and is comprised of a pressure piston 22 and a support piston 24 axially spaced and connected to each other by a tie rod 26 so as to be movable in the chamber 18 as a unit. A pulley 28 is rotatably mounted to the support piston 24 and a pulley 30 is rotatably fixed to the housing 14 within the chamber 18 such that movement of the piston assembly 20 causes the pulley 28 to move toward and away from the pulley 30 .
[0014] One end of the cable 12 is anchored to the housing 14 within the chamber 18 and extends over the pulleys 28 and 30 and from the housing 18 through an opening 32 so that movement of the pulley 28 toward and away from the pulley 30 within the chamber 18 causes the cable 12 to extend from and to retract into the housing 14 through the opening 32 .
[0015] A fluid pressure chamber 34 is formed in one end of the chamber 18 and fluid under pressure is directed into and exhausted from the pressure chamber 34 to cause the pressure piston 22 to move in the chamber 18 causing the pulley 28 to move toward and away from the pulley 30 to extend, retract, and balance the load carried by the cable 12 .
[0016] The piston assembly 20 and the portion of the chamber 18 utilized by the piston assembly 20 as the hoist 10 is being used is considered to be the “power module” of the hoist 10 while the pulley 28 and the portion of the chamber 18 occupied by the pulley 28 as it is moving through the chamber 18 is considered to be the “travel module” of the hoist.
[0017] What has been described to now is conventional in the prior art and forms no part of the present invention. A hoist will now be described which is a considerable improvement over the prior art. The hoist of the present invention, which will become much more apparent as the description proceeds, combines the power module and the travel module into a single unit thus resulting in a less costly hoist requiring less chamber length to achieve the same length of travel for the cable than in prior art devices and requiring less parts and being much simpler in construction and less costly to produce than prior art hoists.
[0018] As can best be seen in FIGS. 2-4 the hoist 110 of the present invention includes a substantially cylindrical housing 112 closed at each end by end caps 114 and 116 to from a substantially cylindrical chamber 118 . The caps 114 and 116 are provided with chain link connectors 120 and 122 respectively which are adapted to be mounted to a rail or the like (not shown) to support the hoist 110 in the workplace.
[0019] A piston 124 is axially slidably mounted within the chamber 118 and is provided with spaced seal rings 126 and 128 to seal the chamber from fluid communication across the piston 124 . The piston 124 is provided with removed portion 130 on the side of the piston 124 facing the end cap 116 and a pulley 132 is rotatably mounted within the portion 130 of the piston 124 so that the piston 124 and the pulley 132 travel together in the chamber 118 .
[0020] A second pulley 134 is mounted in a removed portion 136 of the end cap 116 to be fixed to the end cap 116 but to rotate about an axis parallel to and substantially aligned with the axis of rotation of the pulley 132 . One end 138 of a cable 140 is anchored to the end cap 116 within the housing 112 . The cable 140 extends over the pulleys 132 and 136 and exteriorly of the hoist 110 through the end cap 116 . A seal 141 is provided in the end cap 116 to prevent a pressure leak where the cable 140 extends though the end cap 116 .
[0021] As the piston 124 moves axially in the chamber 118 toward and away from the pulley 134 the cable 140 is extended and retracted from the housing 112 . As can best be seen in FIGS. 3 and 4 the pulleys 132 and 134 are constructed to permit several turns of the cable 140 to be carried by the pulleys 132 and 134 and the length of cable which can be extended from the hoist is determined by the number of turns of the cable 140 provided by the pulleys 132 , 134 .
[0022] The end cap 116 is provided with a connector 142 that provides communication (not shown) through the end cap 116 to the chamber 118 between the piston 124 and the end cap 116 . The connector 142 is connected to a source 144 of fluid pressure, preferably pneumatic pressure, though a valve 146 . The valve 146 is constructed to selectively provide pressure from the source 144 or to exhaust as shown at 148 .
[0023] The end cap 114 is provided with a connector 148 that provides communication through a passage 150 in the end cap 114 to the chamber 118 between the piston 124 and the end cap 114 . The connector 148 is connected to a source 152 of fluid pressure, preferably pneumatic pressure, though a valve 154 . The valve 154 is constructed to selectively provide pressure from the source 152 or to exhaust as shown at 156 .
[0024] It should be apparent that selectively operating the valves 146 and 154 the piston 124 can be moved axially within the chamber 118 to extend and retract the cable 140 and to maintain the load (not shown) on the end of the cable 140 in the desired position. Regulating the pressure against each side of the piston 124 can act to balance the load so that even a heavy load can be moved by hand with minimum effort.
[0025] Also it should be apparent that other controls than those illustrated can be utilized to achieve the desired manipulation of the load in the load balancing hoist of the present invention. The controls are not a part of the present invention. Although pneumatic pressure has been disclosed as the force used to move and to balance the piston 124 , other forms of fluid pressure such as hydraulic pressure could be used as well.
[0026] The construction of the present invention provides a load balancing hoist that has combined the power module and the travel module found in prior art constructions into a single unit. This is accomplished by mounting one of the pulleys that carries the cable to a position within the end cap and the other pulley within and to the piston. This substantially reduces the necessary length of the hoist and substantially reduces the cost of manufacturing a hoist of this type by reducing the number of necessary parts.
[0027] It should also be apparent that although a preferred embodiment of the load balancing hoist of the present invention has been disclosed changes and modifications can be mad to the disclosed embodiment without departing from the spirit of the invention or the scope of the appended claims.
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A load balancing hoist constructed to combine the power module and the travel module of the hoist into a single unit to substantially reduce the cost and the length of the hoist without effecting its operation and application.
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INCORPORATION BY REFERENCE
U.S. Pat. No. 4,122,815 issued Oct. 31, 1978 to same applicant, is incorporated by reference herein as though fully set forth, for the timing method disclosed therein.
BACKGROUND OF THE INVENTION
This invention is in the field of alternating current power sources as used in ignition systems for fuel burning engines.
Prior art systems generally do not involve keying of the AC power source but feed the AC power directly to their igniter circuits. Failure to key such power source results in a low energy level being fed to an igniter by virtue of failure to generate transient currents, highly desireable in such systems.
Should the problem of low energy level ever be resolved, such prior art systems will still fail to perform satisfactorily when AC powered since at higher power and energy levels, the waveforms of voltage and current during firing cycles when not accurately controlled result in successive firing cycle waveforms without any discontinuities therebetween, resulting in pre-ignition of fuel in the engine.
SUMMARY OF THE INVENTION
It is therefore an objective of this invention to provide a high power AC source which is automatically turned off between firing cycles, wherein the energy output of such source is substantially greater than any such source as used in ignition systems.
It is also an objective of this invention to provide means for delivering higher current from the AC power source to an ignition transformer primary winding and consequently delivering higher ignition energy levels.
It is a further objective of this invention to provide switching means of the electronic or other like type which is automatically triggered by a logic circuit, so that energy residual in various parts of the AC power source circuit will be inhibited or not be transferred to the ignition transformer when the AC power source is keyed to its off mode between ignition firing cycles, so that discrete discontinuities between voltage and current waveforms will prevail, and thus ignition timing could be aptly controlled to avoid pre-ignition firing in the engine firing chambers.
Accordingly, a control system is provided for the AC power source with a choice of any of a plural number of electronic switches in various parts of such AC power source circuit to effect such control.
The load fed by the AC power source consists of a transformer having a primary winding coupled to output means of the AC power source. Switching means in the primary circuit is utilized so that when the power source is biased by means of a logic circuit to a quiescent state, the switching means acts to inhibit residual energy in the output means of the AC transformer of the power source from being transferred to the primary winding of the ignition transformer. Such electronic switch is enabled by virtue of the alternating current providing the requisite positive peaks imposed upon the collector of the switch to enable such switch to conduct without the need of the usual DC power feeding such collector. Such switching means may be an electronic switch, generally of the high power and high voltage transistor category. Additionally or alternatively, an electronic switch may be connected between the DC power source used to power the AC source and such AC source, or such switch may be in series with the output means of such AC source. Also, such electronic switch may be in the collector or emitter circuits of the AC source, any of such locations for such switch serving to rapidly cut off energy feed to the load on completion of the ignition cycle, which energy may be residual in the output transformer of the AC power source.
A capacitor utilized in the primary circuit enables power to be transferred to such circuit from the AC power source.
The oscillator stages of the AC power source or any of the electronic switches may utilize Darlington type transistor circuits.
Logic means, coupled to the AC power source and to the switching means, provides substantially simultaneously, bias to the AC power source and to the switching means for turning on the AC power source as well as causing conduction in the switching means.
Various trigger circuits are provided to initiate the logic means, such as a magnetic pulse timer, a cam actuated pair of contactors, an electrically conductive disk with insulative members and a contactor, an optical timer, or a modulated oscillator, any one of which may be coupled to the logic means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of the control system for the AC power source as well as the AC power source itself, showing the logic circuit and utilizing magnetic pulse triggering, according to the invention.
FIG. 2 is a schematic of the same system illustrated in FIG. 1, but having cam actuated contactors as the trigger means or timer.
FIG. 3 is a schematic of the same system as in FIG. 1 except that the cam actuated contactors therein are connected in a different manner than in FIG. 2.
FIG. 4 is a schematic of the same system illustrated in FIG. 1 but having a driven wheel and contactor assembly acting as the trigger means or timer.
FIG. 5 is a schematic of the same system illustrated in FIG. 1 but having an optical trigger means or timer.
FIG. 6 is a schematic of the same system as illustrated in FIG. 1 but having a modulated oscillator as the trigger means or timer.
FIG. 7 is a schematic of an equivalent circuit which represents any of FIGS. 1, 2, 3, 4, 5 or 6, for the purpose making voltage and current measurements by means of an oscilloscope and for enabling the photographing of waveforms so made.
DETAILED DESCRIPTION
Referring to FIG. 1, a high voltage, high current and consequently a high energy AC power source 70 provides alternating current output through its output means 72, which is the secondary winding of a coupling transformer used in source 70. Such source 70 is generally used to power an automotive or like ignition system. This system features an energy inhibit switch electronically controlled by a logic circuit, wherein the inhibit switch may be optionally located in about five different locations in the system. The logic circuit substantially simultaneously turns on the alternating current source and the inhibit switch during the operative period of each firing cycle of the system and turns off the alternating current power source and energy inhibit switch during the non-firing portions or quiescent periods of the system. In FIG. 1, such logic circuit is triggered by a magnetic pulse timer.
In this specification, the conventional ground symbol is shown signifying either negative battery potential of battery 9, DC electrical return paths or AC electrical return paths, and hence such return paths and negative battery potential need not be referred to hereinbelow in explaining the operation of the system.
Accordingly, battery 9, generally of the 12 volt type, provides DC power to the system to make available such DC power at junction 10, and to feed DC power directly to logic circuit 30 and to alternating current power source 70.
Alternating current power source 70 is shown as a transistor type rectangular waveform generator, but it is to be understood that any alternating current source providing for example a saw tooth waveform, a triangular waveform or a sinusoidal waveform may be effectively used to effect this invention, in the circuits of FIG. 1 or in the circuits shown in other figures of this specification.
The magnetic pulse timer, conventional to the automotive field, consists of reluctance wheel 37 having regularly spaced ribs 38 at the wheel periphery, wherein wheel 37 and its ribs 38 are made of a suitable magnetic material and wherein such wheel is driven by distributor shaft 8 which is common to any automotive engine. Such timer employs permanent magnet 34 having a sensor winding 35 thereon. Magnet 34 has pole piece 36 at one end, so that when shaft 8 is driven by the engine, ribs 38 will interrupt magnetic flux lines between ribs 38 and pole piece 36, and induce a voltage in winding 35.
The magnetic timer may be designed with respect to the orientation of the north and south magnetic poles of magnet 34 as well as with respect to the direction of the turns of wire comprising winding 35, so as to provide either a leading negative or leading positive going pulse as an output of winding 35 when one of ribs 38 is driven past pole piece 36. The leading negative pulse design was adopted herein since this is conventional in the automotive industry, and accordingly the components of logic circuit 30 are tailored to recognize such timer pulse. The voltage output in the form of such pulse is fed to logic circuit 30.
Logic circuit 30 comprises a voltage divider consisting of resistors 31 and 32 having a capacitor 33a shunting resistor 32. Such voltage divider is connected to DC power at 10, and resistors 31 and 32 are chosen so that a positive DC potential of about 1.2 volts appears at the junction between resistors 31 and 32 to which one end of winding 35 is connected. Such logic circuit herein utilizes an NPN type transistor switch Q1, the collector of which is connected through resistor 39 to junction 10 so as to provide DC power to switch Q1. The other side of winding 35 is connected to the base of Q1, and such base has capacitor 33b connected between it and ground or the emitter of Q1, which emitter is at ground potential. The function of capacitors 33a and 33b is to filter out and reject AC components riding on the gate pulse appearing between terminal 41 and ground, and initiated by winding 35 due to switching action of the timer when shaft 8 drives reluctor wheel 37. If desired, an additional capacitor 33c may be connected between the base of Q1 and terminal 41 for effecting additional rejection of such timer generated AC components. However, in this system, it may be an advantage to pass such timer generated AC components as they serve to modulate the gate or firing pulse, thereby adding more firing energy by increasing the alternating current output of source 70 by virtue of adding such components to the firing current in transformer 90. In such latter instance, capacitors 33b and 33c may be omitted. Such added components are injected by virtue of switches Q2, Q3, Q4, Q5 or Q7, whichever one of these switches are used. It should also be noted that it would be a simple matter to utilize a PNP type transistor as Q1 logic switch with appropriate changes in the rest of the circuit comprising logic circuit 30. Hence, junction 41 is the point in the system which will change in its potential to enable switching control of the alternating current source 70 and such of the energy inhibit switches Q2, Q3, Q4, Q5 or Q7 as may be used.
Operatively, when shaft 8 is not being rotated or driven by the engine, no voltage is provided by winding 35 to the base of Q1. Under such condition, the base of Q1 will be at a positive potential, sufficient to maintain Q1 in its ON mode, so that junction 41 will be at ground potential. In this case, DC current will flow through winding 35 to maintain the base of Q1 at a positive potential, thereby maintaining Q1 in its ON state, in which case junction 41 is at ground potential thus causing the base of Q2 to be at ground potential as well as the bases of both Q's of source 70, thereby preventing source 70 from oscillating and Q2 from conducting.
When shaft 10 is driven, a pulse having a negative excursion is induced across winding 35 at the time when one of ribs 38 is driven past pole piece 36, providing such negative going pulse to the base of Q1 and turning off Q1, thereby causing junction point 41 to be at positive potential, and under these conditions, turning on oscillator 70 by virtue of positive DC being applied to the bases of the Q's thereof, as well as by turning on switch Q2 by virtue of such same DC positive bias being applied to its base. The manner in which Q2 obtains its collector enabling voltage will be discussed below. The following table shows the switching logic of the FIG. 1 configuration:
______________________________________ State State Potential at State of Potential of of ofShaft 8 Base of Q1 Q1 Junction 41 Q's Q2______________________________________at standstill positive ON ground OFF OFFbeing driven negative OFF positive ON ON______________________________________
Since Q1 is generally a silicon device, it requires a base potential between 0.6 to 0.8 volts to maintain it in its conductive state, and hence the +1.2 volts provided between the junction of resistors 31 and 32 and ground, even considering the voltage drop in winding 35, will still maintain adequate voltage level at Q1 base within the stated limits for minimum sustaining voltage, so that Q1 will be in the ON state when shaft 8 is at standstill as well as when shaft 8 is driven but when ribs 38 are not opposite pole piece 36. In the ON state of Q1, junction 41 will be at ground potential thereby biasing the base of Q2 and the bases of the Q's to cause them to be non-conductive, or in their OFF states.
The divider network consisting of resistors 31 and 32 is chosen so that the voltage at such resistor junction will be 1/10 th the battery voltage. Hence, if the battery or power source charging such battery is defective so that only 8 volts is provided by the battery, there will still be 0.8 volts at such resistor junction which will be sufficient to maintain switching action of Q1 and operate logic circuit 30. Additionally, the manner in which winding 35 is connected in the logic circuit and the large capacitance of capacitor 33a, permitted at its shown location, act to provide a stable source of input voltage to winding 35, and thereby provides a very reliable switching logic circuit.
When shaft 8 is driven and one of ribs 38 is driven past pole piece 36, a negative pulse will be induced in winding 35 which is between 1.5 and 2 volts in amplitude, thereby overcoming the positive bias of the base of Q1 and driving such base negative thereby cutting off current conduction between the collector and emitter of Q1, so that Q1 in switching to its OFF state, will cause junction 41 to be raised to a positive potential so as to turn on the Q's of power source 70 and Q2. The manner in which the Q's of source 70 turn on and off at a particular oscillating frequency or repetition rate is well known in the art and need not be discussed.
When power source 70 is turned on during each firing cycle, that is, each time one of ribs 38 is driven past pole piece 36, such source stays on for the duration when any portion of rib 38 is opposite any portion of pole piece 36, providing the firing gate or firing period at 41 to enable firing of an igniter in an engine, not shown. Power source 70 will keep on generating rectangular waves during such firing gate by virtue of Q1 being in its OFF state and consequently Q2 and the Q's being biased so as to cause Q2 to conduct during such firing gate period and the Q's to oscillate during such firing gate period. By virtue of rotation of wheel 37, when pole piece 36 is positioned between ribs 38, no firing gate is provided because there is absent the required negative going pulse as input to the base of Q1, so that Q1 is again biased sufficiently positive to switch it to its ON state thereby turning off Q2 and both Q's.
Power source 70 has as an integral part thereof a coupling output transformer the design of which controls the frequency or repetition rate of source 70. In this instance, a power source providing a 5 kilocycle rectangular repetition wave was utilized experimentally, the results of which will be discussed below. The output transformer has a center tapped primary winding 71 the ends of such winding being connected each respectively to the collectors of each of the Q's, the emitters of these Q's being at ground potential in a common emitter configuration when Q4 is not in circuit. The oscillator circuit utilizes Q's which are of the NPN type and preferably of the Darlington circuit configuration since such Darlington circuits will have inherently high current amplification characteristics which will provide high induced voltage levels in primary 71. Feedback winding 73 is also center tapped and the ends thereof are respectively connected, one to each base of transistors Q, so as to provide magnetic coupling between windings 73 and 71 and a feedback voltage to maintain oscillation of power source 70. The center tap of winding 73 has bias resistor 74 connected thereto to set the bias current to the proper level for enabling source 70 to be pulsed ON each time junction 41 and consequently terminals 11 and 12 and wire 43 are at positive potential to simultaneously provide proper bias so as to turn on switch Q2. When junction 41 is at ground potential, transistors Q2 and the Q's will be in their OFF states.
It is pointed out that NPN Darlington transistors type 2N6284 made by Motorola were used experimentally as the Q's with excellent performance resulting. It is also to be noted that PNP Darlington transistors of type 2N6287 made by Motorola give similar excellent results. However, with the PNP type transistors, circuit 70 was modified so that the collectors were at negative battery or ground potential, and the emitters were at positive DC potential, and the logic circuit had to be modified to provide the ON and OFF modes discussed above which are compatible with required potentials for the bases of the PNP transistors.
The transformer of source 70 has a secondary winding 72 which provides energy to an external load, such as capacitor 80 and primary winding 91 of transformer 90, as well as being an enabling means to initiate conduction in Q2 by providing thereto a series of positive potentials by virtue of the positive peaks of the waveform generated by circuit 70 during each firing cycle. It is to be noted that DC positive potential to the Q's is provided by virtue of center tap 22 of winding 71 being connected to junction 20, when Q3, Q7 and Q5 are not being used. It is also to be noted that winding 72 is connected to junction 20 when Q3, Q7 and Q5 are not being used. It should also be pointed out that winding 72 connected to junction 20, could have been connected to ground instead, if desired.
Capacitor 80 is coupled to winding 72 at one side, the other side of the capacitor being connected to common terminal 93 of ignition transformer 90. Here too, such other side of capacitor 80 could have been connected to terminal 21, in which case terminal 93 would have been connected to the collector of Q2.
Capacitor 80 is the means for enabling current, and hence power, to be transferred from primary circuit winding 71 through secondary 72 to the load, in this case to transformer primary 91. Without such capacitor the primary current would not be present in sufficient quantity in primary winding 91, and consequently the voltage across primary 91 would be inadequate. Considering that the circuit comprising winding 72, primary 91 and the reactance reflected by secondary 92 when under igniter firing, which is inductive, the capacitive reactance presented by capacitor 80 enables compensation of these inductive reactances resulting in an increased primary current. The resonance principle cannot be used in its entirety to explain the phenomena involving the capacitor's compensation function, since resonance generally involves a single frequency and, consequently unlike here, unique reactance value, and in this system multiple frequencies are generated by power source 70 which involve a like number of different reactances. In any event, such capacitor 80 is selected by trying various values of capacitors until the primary current is at a maximum. Such primary current may be conveniently measured and observed by using a one-ohm high power resistor in the primary winding circuit, say between junction 21 and the collector of Q2, and measuring the voltage across such resistor by means of an accurately calibrated high frequency oscilloscope. Typical capacitor values will be in the order of between 0.2 to 1.0 microfarads.
Ignition transformer 90 was selected to have a turns ratio of 100, somewhat higher than stock automobile transformer turns ratios, since this will provide a greater voltage induced in secondary 92 and transferred to either an igniter or to a switching distributor by means of high voltage cable 94.
A high power, high voltage rated and high current rated power transistor Q2 is used as and inhibit control device. Such transistor may typically be selected from the group of type 2N6251 made by RCA, type 2N6547 made by Motorola, type FT 359 made by Fairchild, or any of a series of Darlington type transistors made by Motorola of the MJ series such as MJ 10009. It is important not only to select a transistor for this purpose which will have a high collector current rating, but such transistor should also be able to withstand the high collector to emitter voltages. Bias resistor 40 of transistor switch Q2 is selected of sufficient ohmic value to limit the base current to a safe level within the rating limits of that transistor, and a bias resistor value is used that permits just enough base current to flow so as to enable Q2 to perform its switching function rapidly. Providing too much base current in Q2 by having too low an homic value for resistor 40 will slow down switching time of Q2 from its ON to its OFF state, and will tend to defeat the major purpose and use of switch Q2.
In a high power system such as illustrated, which approaches 10 kilowatts of instantaneous power, separation of firing waveforms normally are not possible by virtue of the fact that energy generated by source 70 and residual in its transformer windings, will tend to cause the primary current to continue to flow after the Q's of circuit 70 are biased to their OFF states. Consequently, switch Q2 acts to assure rapid deprivation of energy feed to transformer 90 by inhibiting such residual energy from transferring to such transformer at the end of each igniter firing cycle. Such is accomplished in inhibiting the primary current flow at that time by interrupting such current flow in the output circuit by means of rapidly turning off Q2 at the same time as the Q's of source 70 are turned off. The penalty for not having such switch as Q2 in a high power unit is that pre-ignition firing will occur since the next-in-sequence igniter would be prematurely ignited by virtue of the current and voltage waveforms being continued beyond the required firing period.
A cursory examination of the Q2 circuit, would appear to indicate Q2 inoperability in view of no hard wire collector connection to a DC power source. However, as was previously mentioned, Q2 is enabled, that is the equivalent of such DC power is provided to the collector by the positive potential going peak excursions of the waveforms provided by AC source 70. The rate of such excursions, say in the order of between 2.5 and 10 kilocycles per second, though a 5 kilocycle per second rate was actually used, serves to maintain Q2 in its conductive mode throughout each and every igniter fire cycle.
A further benefit may be derived when a Darlington circuit type transistor such as an MJ 10009, MJ10001 or and MJ 10005 by Motorola is chosen as the Q2 transistor. Such Darlington circuit is inherently a current amplifier, so that the current produced by the firing gate to trigger the base of Q2 to its ON state is amplified by Q2 and adds additional current to the current quantity in the primary winding. It should be noted that since the primary current increases, the voltage across primary 91 will be increased by virtue of the increased current flow.
Another feature of the inventive system, including of course the variations of such system as discussed below in conjunction with the other system figures herein, is the quiescent state of power source 70 for about 25% of the system on-time. Inasmuch as Darlington circuits are used for the Q's, high AC currents circulate in their collector circuits in the ON modes of such Q's. Such high currents will contribute to high induced voltages in winding 72, and would normally require large heat sinks to dissipate the heat generated thereby. Since in this power generator, each of the Q's is in its ON state only half the time of each cyclic excursion of the AC current produced therein, and since each igniter firing period is less than one-half its non-firing period in time duration, triggering bias winding 73 in order to turn the Q's on and off, will permit the transistors to be maintained at relatively low operating temperatures because each of the Q's will in effect have a duty cycle of less than 25%. Further, switching such power source 70 to its ON mode will create a transient voltage at the beginning of each firing cycle which will be greater in amplitude than the voltage normally deliverable by such source 70, absent this type of switching.
The foregoing discussion related to the case where Q2 was used as the energy inhibit switch. Such foregoing discussion assumed that when Q2 was so used, Q3, Q4, Q5 and Q7 were not in the FIG. 1 circuit. Accordingly, with Q2 performing the energy inhibit function, Q3, Q4, Q5 and Q7 are removed from their sockets and electrically by-passed. Q3 is by-passed by electrically connecting terminals 19 and 22. Q4 is by-passed by connecting its socket collector to ground. Q5 is by-passed by connecting its socket collector terminal to terminal 19. Q7 is by-passed by connecting terminal 19 to the emitter terminal of its socket. The base circuits of the foregoing by-passed transistor switches under these circumstances will have no affect since they will be electrically open circuited. It will be understood, without further statements, that only one of the group of Q2, Q3, Q4, Q5 or Q7 switches will be in circuit at any one time, all others will be by-passed as stated in the above switch by-passing examples, and when Q2 is by-passed terminal 21 is connected to ground, with Q2 removed from its socket.
With this in mind, it can be seen that when Q3 is operative, all other transistors performing the energy inhibit function will be by-passed, and in such case base current to Q3 will be provided by virtue of electrical connection 13-14 to base current limiting resistor 75. The collector of Q3 will be connected to terminal 19, which under by-pass condition of Q5 will be electrically at terminal 20, the positive DC potential feed from battery 9 of the system. The emitter of Q3 will be connected to center tap 22 of winding 71. Operationally, Q3 will be keyed on and off for each ignition cycle, as discussed for the case of Q2 above by means of logic circuit 30, so as to turn off DC power to the collectors of the Q's and thereby inhibit energy from being transferred to transformer 90 at the end of such ignition firing cycle.
When Q4 is used as the energy inhibit switch, then Q2, Q3, Q5 and Q7 are by-passed. In such case, the collector of Q4 is connected to the emitters of the Q's and the emitter of Q4 is at ground potential, and the base of Q4 is connected through its bias resistor 76 to cable 15-16 which is at the same potential as terminal 41 of Q1. Such connection of Q4, switches the emitters of the Q's on and off by interrupting current flow in the emitter circuit of such Q's.
When Q5 is used as the energy inhibit switch, then Q2, Q3, Q4 and Q7 are by-passed. In such case, the collector of Q5 receives its positive DC potential from terminal 20, the emitter of Q5 by virtue of by-pass of Q7 will feed one end of winding 72, and the base of Q5 is connected through bias resistor 78 to cable 17-18 which is at the same potential as terminal 41 of Q1. Such connection of Q5 switches off any residual energy stored in winding 72 from being transferred to the ignition transformer after the ignition firing cycle is terminated, as well as disconnecting DC power from source 70 at that time.
When Q7 is used as the energy inhibit switch, then Q2, Q3, Q4 and Q5 are by-passed. In such case, the collector of Q7 will be at the potential of terminal 20 which the DC positive potential provided by battery 9, the emitter of Q7 will be connected to winding 72, and the base of Q7 will be connected through its bias resistor 79 to cable 23-24 which is at the same potential as terminal 41 of Q1. Such connection of Q7 will prevent any residual energy stored in winding 72 from being transferred to the ignition transformer after the ignition firing cycle is terminated.
The use of Q7 as the energy inhibit switch as well as the use of Q5, provides the lowest collector to emitter voltages, but have the detriment of not having the ignition transformer primary winding 91 in their collector circuits, with no attendant advantage of current amplification, as compared with Q2 switch circuit.
The use of Q3 or Q4 for the energy inhibit purpose is quite effective, but use of either such switch in these particular parts of the circuit serves to drop the DC voltage fed to the primary circuit of the AC power source with attendant drop in power output from such AC source.
Referring to FIG. 2, the system illustrated is identical to the systems as discussed in connection with FIG. 1, except that circuit 30 is replaced by circuit 30a.
Circuit 30a used a conventional cam actuated pair of contactors wherein engine distributor shaft 8 drives cam 51, the high portions of which cause the cessation of cooperation between contactors 49 and 50. When the high portions of cam 51 are not in cooperation with contactor 50, such contactor will cooperate with contactor 49. Contactor 49 is connected to junction 47, which junction is also the base of transistor switch Q1, electrically speaking, and Q1 is the same switch as used in FIG. 1. Resistor 46 provides a DC positive potential to junction 47 when contactor pair 49-50 are open, and thus enables base current in Q1 to flow. When contactor pair 49-50 are closed, junction 47 is at ground potential. The collector of Q1 is connected through its resistor 48 to the DC positive feed at terminal 20, fed by battery 9 by virtue of its connection to junction 10. The emitter of Q1 is at ground potential. Thus terminal 41 provides the same gate thereat as in FIG. 1 and supplies switching potentials to terminals 11, 13, 15, 17 and 23. The following table summarizes the switching logic of circuit 30a.
______________________________________ State StateContactor Potential at State of Potential at of ofPair 49-50 Junction 47 Q1 Junction 41 Q's Q2______________________________________open positive ON ground OFF ONclosed ground OFF positive ON ON______________________________________
Hence, when cam 51 causes contactors 49-50 to cooperate, the base Q1 is biased at ground potential, collector current does not flow in Q1 and Q1 does not conduct. When cam 51 causes contactor pair 49-50 to open, ground is removed from junction 47 and base current flows in Q1 and Q1 conducts thereby providing ground potential at junction 41. Such ground potential biases Q2 and the Q's to their OFF states. When Q1 does not conduct, junction 41 will be at a positive potential thereby causing Q2 and the Q's to be turned ON due to the base currents flowing in Q2 and the Q's.
Thus it can be seen that the logic circuit and the timer as herein illustrated may be utilized in the circuit of FIG. 1 instead of the timer shown therein, and yet maintain all the same functions and operations of the system as heretofore discussed. The functions performed by Q2 may be performed by either Q3, Q4, Q5 or Q7 as above described, but in conjunction with circuit 30a instead of circuit 30.
Referring to FIG. 3, the system illustrated is identical to the system as discussed in connection with FIG. 1, except for circuit 30 being replaced by circuit 30b.
Circuit 30b is identical in structure and function to logic circuit 30a described in connection with FIG. 2, except that the collector is connected directly to the positive DC source and a resistor 52 is connected between the emitter of Q1 at junction 42 and ground. Thus junctions 11, 13, 15, 17 and 23 are connected to junction 42 in FIG. 3 as compared to being connected to junction 41 of FIGS. 1 or 2. The FIG. 3 structure will function in the same manner as FIG. 2 structure, except the logic thereof will be as follows:
______________________________________ State StateContactor Potential at State of Potential at State of State ofPair 49-50 Junction 47 Q1 Junction 42 Q's Q2______________________________________closed ground OFF ground OFF OFFopen positive ON positive ON ON______________________________________
The discussion in connection with the use of Q3, Q4, Q5 or Q7 as the energy inhibit switch, instead of Q2, as discussed in conjunction with FIG. 1, applies here when circuit 30b is used in lieu of circuit 30.
Referring to FIG. 4, it can be seen that circuit 30c therein is functionally the same as circuit 30b, except that instead of cam actuated contactors a disk 53 driven by shaft 8 is used in cooperation with a contactor 55 which cooperates with the disk periphery, and which contactor is connected to junction 47. Shaft 8 being at ground potential will electrically ground the metallic portions of disk 53. Disk 53 has a plural number of electrically insulative members 54 regularly spaced at the periphery of the disk within the disk confines. The number of members 54 will be equal to the number of igniter circuits as provided by a high voltage distributor, not shown, but conventional. Here, four igniter circuits and corresponding four igniters, one for each of the four engine cylinders is assumed by virtue of illustrating four insulating members 54. When an insulative member 54 is in cooperation with contactor 55, the base of Q1 being at the same potential as junction 47, is biased with a positive DC potential and Q1 conducts thereby providing a positive potential at its emitter at junction point 42, consequently providing such positive bias to junctions 11, 13, 15, 17 and 23, thereby turning on Q2 and the Q's to perform the functions as hereinabove described in connection with FIGS. 1 or 3. When contactor 55 is in cooperation with the metallic or conductive portions of disk 53, junction 47 is at ground potential, Q1 does not conduct, and junctions 11, 13, 15, 17 and 23 are at ground potential, thereby turning off Q2 and the Q's, or in the case of Q3, Q4, Q5 or Q7 turning off those transistors. The following logic table is applicable to show the logic of FIG. 4 configuration:
______________________________________ State State StateContactor 55 in Potential at of Potential at of ofCooperation With Junction 47 Q1 Junction 42 Q's Q2______________________________________metallic portion ground OFF ground OFF OFFof disk 53member 54 positive ON positive ON ON______________________________________
The discussion in connection with the use of Q3, Q4, Q5 or Q7 as the energy inhibit switch, instead of Q2, as stated in connection with FIG. 1 discussion, applies here when circuit 30c is used in lieu of circuit 30.
Referring to FIG. 5, the system illustrated is identical to the system as discussed in connection with FIG. 1, except that trigger circuit 30 is replaced by an optical trigger and logic circuit 30d.
Circuit 30d comprises a disk 57 driven by distributor shaft 8. Disk 57 has apertures 58 regularly spaced in the disk at the periphery thereof. Powered illumination means 56 is provided at one face of disk 57 for optically intermittently illuminating the base of an optically sensitive transistor Q6 by means of a light beam 59 impinging on the base of Q6 and thereby causing the emitter of Q6 at junction 42 to rise to a positive DC potential by virtue of collector current flowing in Q6. When light beam 59 is blocked by the opaque portion of disk 57, Q6 is off and no collector current flows in Q6, and consequently the potential at either end of resistor 52 is the same, namely ground potential. Hence, when Q6 is in its OFF state, junctions 11, 13, 15, 17 and 23 will be at ground potential, maintaining Q2 and the Q's in their OFF states. On the other hand when Q6 is in its ON state, junctions 11, 13, 15, 17 and 23 will be at positive DC potential maintaining Q2 in its ON state and the Q's in their oscillatory modes. The following table shows the logic of the FIG. 5 configuration:
______________________________________ State Potential at ofLight Beam 59 State of Q6 Junction 42 State of Q's Q2______________________________________blocked by OFF ground OFF OFFdisk 57passes through ON positive ON ONaperture 58______________________________________
The discussion in connection with the use of Q3, Q4, Q5 or Q7 as the energy inhibit switch instead of Q2 as discussed in connection with FIG. 1, applies here when circuit 30d is used in lieu of circuit 30.
Referring to FIG. 6, the system illustrated is identical to the system as discussed in connection with FIG. 1, except that circuit 30 is replaced by circuit 30e.
Circuit 30e employs an angular modulated oscillator wherein oscillator 60 is modulated by virtue of a variable capacitor being driven by distributor shaft 8. Such capacitor comprises a rotatable plate 63 having protrusions 62 regularly spaced at the periphery of plate 63, and having a single fixed plate 61 connected to oscillator 60. Plate 63 is at ground potential since it is attached to shaft 8 which is grounded. Oscillator 60 provides a positive going signal output imposed upon the base of Q1 whenever a protrusion 62 is driven past fixed plate 61. More details concerning this modulation method is available in U.S. Pat. No. 4,122,815 issued Oct. 31, 1978 which was incorporated by reference herein.
Logic circuit 30e has a bias resistor 64 connected between the base of transistor Q1 and ground, so as to maintain the base at ground potential until such time as a positive signal from oscillator 60 drives the base sufficiently positive to cause base current to flow and hence to cause collector current to flow and Q1 to conduct.
The emitter of Q1 has resistor 52 connected between it and ground, so that when the base of Q1 is at ground potential and no collector current flows, the emitter of Q1 and junctions 42, 11, 13, 15, 17 and 23 will be at ground potential thereby maintaining Q2 and the Q's in their OFF states. When a positive going signal from oscillator 60 appears at the base of Q1 due to the oscillator being angularly modulated, the base of Q1 will be driven positive and base current will flow to cause Q1 to switch to its ON state, thereby raising the emitter of Q1 at junction 42, as well as raising junctions 11, 13, 15, 17 and 23 to a positive DC potential and causing Q2 to be switched to its ON state and the Q's to oscillate. The following table expresses the logic performed by the FIG. 6 configuration:
______________________________________ State State Potential at State of Potential at of ofOscillator 60 Base of Q1 Q1 Junction 42 Q's Q2______________________________________not modulated ground OFF ground OFF OFFangularly positive ON positive ON ONmodulated______________________________________
The discussion in connection with the use of Q3, Q4, Q5 or Q7 as the energy inhibit switch as discussed in connection with FIG. 1, instead of Q2, applies here when circuit 30e is used in lieu of circuit 30.
Referring to FIG. 7, the equivalent circuit for each of the configurations of FIGS. 1, 2, 3, 4, 5 or 6, may be represented by such FIG. 7, set up in the laboratory so as to enable actual waveform photographs to be made, and to enable actual measurements to be made of the ignition transformer primary voltage and current.
It is obvious from FIG. 7 that such figure uses the timer and logic circuit for the system of FIG. 2. However, the measurements of voltage e and current i, are equally applicable to the other configurations.
In this test set up, a conventional high voltage distributor 95 was driven by an electric motor driving shaft 8, thus driving cam 51 and distributor rotor 96. Igniters 98 were connected to the stationary members 97 of distributor 95.
The table below, shows peak-to-peak values of voltage e across primary winding 91 and peak-to-peak values of current i through such primary winding, as measured by a calibrated Hewlett-Packard 50 megacycle oscilloscope. The oscilloscopic patterns of the current were made by inserting a high power one-ohm resistor in series with the primary winding and connecting the oscilloscope input leads thereacross. By Ohm's law, the voltage measured will be the current, since such voltage is divided by one-ohm. This table shows the voltages and currents under conditions when both Darlington type transistors and when non-Darlington type transistors are used in the Q2 switch, or alternatively in the Q3, Q4, Q5 or Q7 switches. FIG. 7 configuration was used for these laboratory tests, wherein a conventional distributor was connected to the secondary winding 92 and in turn the distributor was connected to a number of igniters. Such distributor was driven by an electric motor at a speed simulating medium distributor rotation speed in an automobile. The following table shows the results of measurements made:
______________________________________ Non-Darlington Q2, Darlington Q2,Parameter 2N6251 or 2N6547 MJ 10005 - Motorola______________________________________i (peak-to-peak) 8.33 amperes 12.5 amperese (peak-to-peak) 1200 volts 1330 voltsP = ie 9996 watts 16,625 wattsE.sub.primary 2.08 watt-seconds 3.46 watt-secondsE.sub.igniter 1.87 watt-seconds 3.12 watt-seconds ##STR1## 200 333______________________________________
ε primary , the energy in the ignition transformer primary winding was computed using a firing period of t=0.833 milliseconds, the firing period for an igniter in an 8 cylinder engine driven at 6000 revolutions per minute, and including the duty cycle for the voltage wave and current wave provided by the AC source of T=0.5 each, therefore ε primary =PtT 2 .
ε igniter is the energy in the secondary winding of the ignition transformer and hence the igniter firing energy, which is the energy in the primary winding multiplied by the ignition transformer transfer efficiency η=0.9, therefore ε igniter =ηε primary .
Here, the difference between the use of Darlington Q2 switch and a non-Darlington switch becomes evident in terms of the increased voltage and current and consequently in terms of instantaneous power and energy levels.
However, when Q2 or any of these other like switches are not in circuit, or by-passed, the results obtained are as indicated in the above table. Such results indicate that there is residual energy stored in the coupling transformer of the AC power source and transfer of such residual energy to the ignition transformer primary after the timer of the system and its logic circuit in operation had biased the Q's of the AC source to their non-conducting states. Such residual energy is cut off by Q2 control, or the other like mentioned switches, simultaneously with deactivation of the AC source, as hereinabove explained, the Q2 switch serving to inhibit current flowing, due to residual energy in the coupling transformer, at the end of each igniter firing period.
It also becomes evident from the foregoing, that Q2 utilized to control igniter firing energy, also functions to increase the energy level of the system by its switching and by amplifying the firing gate current, as such amplified current is added to the current provided by the AC power source.
A comparison with a conventional Kettering system, utilizing an igniter of conventional type with its spark gap setting in accordance with automotive manufacturer's specification, may be made with the performance of an igniter in the inventive system. The conventional Kettering system was set up in the laboratory with a driven conventional distributor similar to the laboratory set up for the inventive system as discussed above. The difference in performance between the Kettering system, as photographed, with the inventive system in terms of arc area coverage and energy delivered to ignite the engine fuel, is rather startling, and self evident from the results obtained.
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An alternating current power source which is generally used to feed an ignition transformer primary winding may be electronically controlled so as to rapidly activate and deactivate the power source for each ignition cycle. An electronic switch intermittently interrupts current flowing in the primary winding and in the output circuit of the power source. Such electronic switch is made operable by virtue of the peak excursions of the alternating current, thus supplying the necessary collector potential to such switch during each firing cycle of the system. Such control system can have these type of controls in the collector circuit of the power source, the emitter circuit of such power source, the DC power input circuit for such power source, or in the output circuit of the power source's output transformer. A capacitor in series with the output circuit of the power source and with the primary winding enables current to be transferred out of the power source to such primary winding. Such electronic switch will provide discrete separation between successive output waveforms of successive ignition firing cycles. The system has appropriate logic circuits which initiate current conduction through the electronic switch and in the oscillator stages of the power source for each firing cycle, turning off the switch and oscillator stages between firing periods. Various types of trigger timing circuits are usable to trigger the several logic circuits for initiating igniter firing by means of the resultant high voltage and high current in the secondary winding of the ignition transformer.
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FIELD OF THE INVENTION
This invention relates to ski boots, and to attachments or extensions for ski boots, specifically designed to permit the user to wear the ski boot while skiing and also to use the ski boot while walking, obviating the existing problems with ski boots during walking.
BACKGROUND
Over the past twenty years, it has been discovered that an active and mobile ankle hinders the art of skiing, because the ankle is not designed to control the massive forces created by the long lever-arms of the skis. The problem has been solved with the high-top ski boot which has totally immobilized the foot and ankle. Recent improvements have served to eliminate the last vestiges of motion of the skier's foot. The results have been wonderful on the slopes with the skis on, but walking in these ski boots has presented very serious problems and disadvantages. The present invention is directed to an improvement in the sole construction, or adaptation for use with a sole construction, of the type of ski boots just referred to which maintains solid fixation of the foot and ankle.
The tibio-talar joints and subtalar joints, together comprising what is commonly known as the ankle joint, in man performs three functions. They allow for controlling the absorption of impact after heel-strike. They allow for the advancement and rotation of the leg without the foot having to slide, or leave the floor, and allow the body weight to rest over the most stable, strongest of the foot during rest. The functions of the ankle, the foot, the lower leg and the knee, and various particular structures within these members are discussed as they relate to the design of the subject invention. In this discussion, the following terms are used and have the definition given below:
Contact Point: The contact point, as you see here, is the point of initial contact during normal walking, used at the rear most tip of the heel.
Resting Surface: The resting surface of the boot, or the boot sole, is that portion which is in contact with the floor or ground during normal standing. (The terms floor and ground are used interchangeably throughout this specification and the claims to indicate a normal walking surface, whether indoor or out, and include walking on snow, or in any other place where walking may occur.)
Incident Angle: The incident angle referred to hereinafter is the angle the leg makes to the floor during initial contact of the foot with the floor.
Center of the Knee: The center of the knee is the center of pressure for weight-bearing in the knee. The center of the knee is approximated by finding the center of the proximal end of the tibia.
Vector Point: The vector point is the center most point of the area in which force is exerted at any instant in time against the floor, resolved into a single vector with its origin upon the floor. In order for a man to stand, this vector must pass through a weight-bearing portion of the foot. The vector point is defined as the origin, on the floor, of this vector. During walking, of course, the vector point moves from the rear or posterior end of the sole to the front or anterior end of the sole as the foot rolls from the heel, upon striking, to the toe as the weight is transferred to the other foot.
Central Line: The central line is defined as an imaginary line passing perpendicular to the floor through the medial malleolus of the user's foot.
Medial: Medial and medially refer to the inside of the foot. Thus, the medial side of the right foot of the user would be on the left side of the foot whereas the medial side of the left foot of the user would be the right side of the foot.
Lateral: The terms lateral and laterally refer to the outside of the foot.
Malleolus: The malleolus is the outcropping which is commonly referred to as the ankle.
Segment: A segment, as used here, approximates about thirty percent of the length of the foot, but is defined as the distance from the heel of the user to the central line, as defined above.
Metatarsal: Metatarsal refers to the high metatarsal bones which form the skeleton of the foot which articulate with the tarsal bones and with each other proximally and distally, articulate with the proximal end of the phalanx. The metatarsal head is the enlarged portion of the foot where the metatarsal bones articulate with the phalanges.
Reference may be made to standard texts or treatise for other definitions of body structures. See, for example, HUMAN ANATOMY AND PHYSIOLOGY, Alexandra P. Spence and Elliott B. Mason, The Benjamin/Cummings Publishing Company, Inc. 1979.
There have been numerous attempts to solve the problem of walking in ski boots. Representative of these attempts are the structures disclosed in the following United States patents.
Booty U.S. Pat. No. 4,286,397, 9/1/1981
Brugger-Stuker U.S. Pat. No. 3,971,144, 7/27/1976
D'Alessandro et al U.S. Pat. No. 4,045,890, 9/6/1977
DeFever U.S. Pat. No. 4,156,316, 5/29/1979
Frey U.S. Pat. No. 4,199,880, 4/29/1980
Groves U.S. Pat. No. 4,228,602, 10/21/1980
Kastinger U.S. Pat. No. 4,194,309, 3/25/1980
Keller U.S. Pat. No. 4,294,025, 10/13/1981
Pasich U.S. Pat. No. 4,123,854, 11/7/1978
Sartor U.S. Pat. No. 4,291,473, 9/29/1981
Sturany U.S. Pat. No. 3,740,873, 6/26/1973
Viletto U.S. Pat. No. 4,261,114, 4/14/1981
Weninger U.S. Pat. No. 4,155,179, 5/22/1979
Woolley U.S. Pat. No. 4,160,301, 7/10/1979
The above patents disclose a great variety of attachments and modifications of ski soles and ski boot constructions designed to alleviate the difficulty in walking occasioned by the design of the ski boot which, of course, is designed primarily to be comfortable during skiing and to permit the skier maximum control of the skis. The Frey patent discloses an attachment for ski boots as do the patents to Booty, Groves, Woolley, DeFever, Pasich, D'Alessandro et al, Brugger-Stuker, Keller and Sturany. The patents to Sartor, Kastinger and Weninger, each discloses ski boots which have a portion which can be moved to provide a non-flat ski sole and the patent to Viletto discloses a ski boot with a sole which has a bendable portion formed therein.
While the problem of walking in ski boots is well recognized and while many efforts have been made to solve the problem, it does not appear that a solution has been found and a boot sole designed to meet the fundamental bases of the problem. Generally, the prior art has concentrated upon providing some kind of a walker device either built into or attached to the ski boot providing a higher center than ends, permitting the skier, the user, when he is walking to rock from one end of the boot to the other. No recognition of the actual rocking mechanism of the foot and angular relationships are shown to have been considered in these designs. It is an object of this invention to provide a ski boot with a sole extension, or a sole extension which is adapted to be associated with a ski boot, which is designed to permit the skier to walk comfortably and efficiently, with minimal unnatural movement of the legs, ankles and foot.
SUMMARY OF THE INVENTION
The present invention relates to a ski boot which has a specially designed body and sole construction. The ski boot of this invention comprises a body which has an upper surface configured to mate with the sole structure of the boot combined with a specially designed sole. The body is formed unitarily with the sole, the sole being elongate, having a length and a width generally corresponding to the length and width of the user's foot. The bottom of the sole is formed and configured into at least three, preferably four, portions. The first portion is adapted to rest on the top of the ski during skiing. The first portion is generally flat and lies under the metatarsal and partially under slightly up-turned toes of the user's foot. It may begin slightly posterior to the metatarsal head, when the user is skiing, and extends anterior thereto and may extend partially under the toes. The second portion slopes in a complex double arcuate or curved configuration, curving longitudinally and medially of the user's foot forwardly from the first portion and upperly toward the top of the boot toe. The third portion slopes in a generally flat configuration rearwardly from the first portion to at least a point approximately under the medial malleolus of the user's ankle. The fourth portion slopes in a double arcuate or curved configuration laterally of the user's foot and rearwardly thereof, toward the upper surface such that, in use, the fourth portion normally strikes the floor first when the user is walking. The four portions of the bottom form a continuous surface which is constructed and configured such that the user's foot rolls laterally on the fourth portion, after striking, to the third portion, whereupon it rolls along the third portion and then the first portion, generally centrally, and then rolls medially on the second portion as the user ends a stride.
The rear most end of the sole preferably lies approximately one-half the distance from the tip of the user's heel (the rear most point of the heel of the user when the boot is in use) to a point lying directly below the medial malleolus of the user's ankle.
The front most end of the first portion extends approximate a point approximately beneath the metatarsal head of the user's foot (when the boot and body are in use) to the anterior of the toe, and slightly beyond.
The first and third portions are, preferably, generally planar, though this is not critical, and intersect each other, the angle between the planes of the first and the third portions generally being from about five degrees to about fifteen degrees, usually in the range of about ten degrees. For certain professional skiers, this angle may be as high as twenty-five or even thirty degrees, but for most skiers, angle in the vicinity of about ten degrees plus or minus five degrees is preferred.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a generalized depiction of a prior art ski boot worn by a wearer showing its position during walking.
FIG. 2 is a depiction of a prior art ski boot, as shown in FIG. 1, showing the configuration during skiing.
FIG. 3 is a schematic depiction of the present invention, being used in the walking mode.
FIG. 4 is a schematic depiction of the present invention being used in the skiing mode.
FIG. 5 is a bottom view of the configuration of the sole.
FIG. 6 is an exploded view showing the relationship of the ski boot of this invention to a ski.
FIG. 7 is a side view showing the ski boot of this invention, in cross-section, as it would rest upon a ski.
FIG. 8 depicts a partial cross-section of the sole of the boot of this invention taken along lines 8--8 in the direction of the arrows as shown in FIG. 7.
FIG. 9 depicts a partial cross-section of the sole of the boot of this invention taken along lines 9--9 in the direction of the arrows as shown in FIG. 7.
FIG. 10 depicts a partial cross-section of the sole of the boot of this invention taken along lines 10--10 in the direction of the arrows as shown in FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A perpendicular drawn up from the floor, passing through the medial malleolus will roughly pass through the dome of the tallus. This is called the central line. The lateral malleolus is formed by the head of the fibula which is posterior to the dome of the tallus. This means that the dome of the tallus can be palpated laterally just anterior of the lateral malleolus. This is the lateral determiner for the central line.
If a person could balance their weight perfectly so that the vector point, the center of the knee and the medial malleolus were all on the central line, then no muscle action would be required or balance to be maintained. Normally, the vector point for standing falls anterior to this line, so that minor amounts of calf muscle tension are required for balance. By varying the tension in the calf, the body can control the exact standing attitude or posture. The distance between the central line, i.e., the point where the central line would intersect the floor, posteriorly of the central line to the rear most point of the heel of the user is defined as one segment. The naked foot naturally divides itself into approximately equal, functional, segments. The distance from the central line to the most posterior segment of the foot is about thirty percent of the total lateral length of the foot. This is one segment. From the central line to a point just behind the metatarsal heads is about one and one-half segments, corresponding to about forty-five percent lateral length of the foot. The metatarsal heads and the toes comprise slightly less than one segment, about twenty-five percent of the lateral length of the toes. The first phangie of the halix is about one-half segment. The sole of the ski boot, and the sole extension of this invention, are designed to accommodate segments relative to the naked foot.
To describe the sole construction of the boot of this invention, it is convenient to start at the back and work forward, for this is how the floor "sees" the sole during normal ambulation.
The first feature of this invention of note, proceeding in this form of the description, is that the heel of the sole extension is cut away. The heel contact point of the sole extension is approximately one-half segment forwardly of the heel of the user. The force, or torgue, placed upon the foot is a product of the weight of the step times the distance from the central line. Thus, if the sole extension is cut away, the torgue is reduced. If the cut away portion were to extend forward to the central line, then no torgue would be imparted to the foot during the heel-stride. While this would be desirable, from one sense, it would result in undesirable effects, which will be discussed later. Briefly, it would result in a less stable resting surface during normal standing.
A point one-half segment posterior to the central line is the principal contact. Selection of this principal contact point will decrease the ankle torque by about one-third of the normal ambulatory value. The decrease of ankle torque is to less than one-half the original torque because the heel of the standard ski boot extends far beyond the naked heel. This means that one-half segment behind the central line will be about one-third of the distance to the most posterior point on the boot. Cutting the heel further will cause instability while standing.
It would be desirable for all soles to be of equal heights. This would make adjusting the skiis from boot to boot far simpler. It appears, however, that three standard heights would be feasible and desirable; one for men, one for women, and a children's size. This would be important only in determining the block height on the skiis to permit the boot to be properly secured to the skis. It should be noted at this point that any type of ski binding may be used with this invention. Only the height about the ski of the binding need be adjusted.
Thickness of the sole extension can be determined from the constraints already set forth. The height of the heel - block on the ski is arbitrary, but once selected, dictates the angle of the flat second, main weight-bearing portion of the ski during skiing. This articulates with the third main weight-bearing portion during standing in a rounded manner a fixed distance of one segment anterior to the central line. It should be noted that the toes are bent up (dorsiflexed) from the metatarsal heads so that the boot may be designed more with the ankle less dorsiflexion, and the mass of the sole extension can be minimized.
Variation between different boot sizes and requirements can be compensated by the one-half segment behind the central line. The slope and degree of curvature in this segment is not critical. It can, therefore, act as a connector between the heel contact point, in which height is critical, and the flat, sloping segment immediately anterior to the central line, i.e., the standing surface. The height here is determined by its mandated angle perpendicular to the central line, and the surface inersect with the next flat segment. The slope and degree of curvature from under the metatarsal heads to the toe of the boot is not critical.
The normally walking individual's leg forms an angle of about sixty-five degrees to the floor during the heel strike. The military calculates that during a forced-march, this angle approaches forty-seven degrees and the military tests the boots accordingly. An angle of sixty degrees has been selected for the walking ski boot of this invention such that it will have its heel contact points so that user's leg will be at an angle of about sixty degrees with the floor. This would allow for a comfortably long stride. If this user stretches his stride further, the back of the boot may strike the floor. This is compensated for by providing a soft non-skid rubber surface on the back of the boot. This is largely simply an abundance of caution, but is considered a feature of the invention. The second effect is that the high ankle torgue previously mentioned will be invoked to rotate the boot onto the floor, thus aiding greatly in preventing slippage and falls.
The one-half segment between the heel contact point and the central line is rounded to ease the progression of the body weight forward. It is also lower laterally than medially, with slight rounding in that plane. That is, this portion of the sole extension is generally arcuate, (not necessarily part of a circular arc) being curved in two dimensions, laterally and longitudinally. The purpose of this angulation is to cause the foot to stride in a valgus, pronate position. Thus the sole is leveled, medially and laterally equal, at the central line, the boot and foot will be forced to supinate as the weight progresses forwardly. This supination will compensate for the natural rotation of the hip during normal ambulation.
The next segment is medially-laterally leveled, i.e., is substantially flat and is generally parallel to the keel of the ski boot such that during standing, a line perpendicular to the floor passes through the center of this resting surface, this segment, and through the center of the knee.
Progressing to the next segment, this surface is designed to support the ski boot on the ski and is generally flat and at an angle to the keel of the boot. It is preferably slightly longer on the medial side of the boot than the lateral. The purpose of this segment is to provide solid support while skiing. In combination with heel and toe posts, rigid control of the ski is achieved of acceptable strength for all but the most advanced competition skier. Those few skiers who desire additional control strength can place additional blocks upon their skis so as to support the sole extension on the ski along much of its length.
In mounting this ski boot onto the ski, the heel post is a block mounted on the ski to fit under the heel cut away portion and give support while skiing. The toe post is an analogous block placed under the cut away under the toes. Thus, the heel, the toes and the metatarsal of the user's foot are supported directly by the ski, during skiing.
Thus, reviewing very briefly, as the user walks, the rear most or fourth portion of the bottom of the sole is contacted, being cut away so as to be about one-half segment forwardly of the rear of the heel of the user, the force vector of the user's weight moves forwardly and medially to about the center and then moves forwardly along a line generally along the center of the body as the user walks further, and, finally, as the user moves off the boot, the force vector of the user's weight moves forwardly and medially toward the medial side of the user's foot underneath the first phalanx.
During normal standing, the vector point falls between the central line and the metatarsal heads. This is virtually all of the time when an individual is standing, therefore, if no support were provided posterior to the central line, then most of the time there would be no problem. However, if the user tended to tip back, if the weight were ever to fall behind the central line, there would be some instability because the ankle is firmly fixed and weighted by the boot. and the ability of the user to recover is greatly diminished. By placing the initial contact point one-half segment behind the central line, a firm platform is provided for those rare instances when the vector point may fall behind the central line and, therefore, there is an opportunity to recover before falling.
With these design and function criteria in mind, reference will be made to the drawings and to the preferred embodiment of the invention, with the understanding that this is simply a preferred embodiment. The invention can be made of any material of suitable physical characteristics, and can be made in many different shapes and a virtually infinite variety of sizes, so long as the principles described are followed, without departing from the intent and scope of the invention.
Modern ski boots are frequently made in an essentially unitary construction. The manufacturing process is sometimes accomplished in steps but the end result is often a ski boot comprised of a polymeric material in which the uppers and the sole are substantially integral one with another. In the embodiment depicted here as exemplary, this construction is adopted. It should be understood, clearly, however, that the soles may be made of one plastic, or of leather, and the uppers made of another plastic, or of leather, or of some other material. Commonly used plastics, i.e., polymeric materials, such as the polyvinyl polymers and copolymers, polycarbonate polymers and copolymers, and others, may be used, as is traditional in the industry at the current time. Thus, the materials of which the ski boot of this invention is made is of no consequence particularly so long as the configuration described and claimed is reasonably adhered to.
FIG. 1 and FIG. 2 show a typical prior art ski boot, in largely schematic depiction showing the position during walking and during skiing. During skiing, the user's knees are bent to some degree and he skis in a crouch or partially crouched position. The ski boot is designed to provide this feature. During walking, however, the knees ae traditionally straight, except during taking the stride, and, therefore, the traditional ski boot puts unusual forces on the user's legs, ankles and fee.
FIG. 3 shows the boot of the present invention in largely schematic form, during walking and shows that the force factor which extends through the knee of the user is substantially perpendicular to the floor or ground when the user is standing. This, of course, is the usual and proper standing position.
FIG. 4 depicts the boot of this invention, in schematic form, lash to a ski showing that, during skiing, the knee is bent, as is the proper skiing posture. It will be noted that the toes are slightly flexed. While not critical to the major advantages of the invention, this is a very important feature. While presenting a very minor discomfort when walking, this feature makes for great comfort and control during skiing. The under-side of the foot at the metatarsal head and of the toes is generally parallel to the plane of the first portion 110 of the boot sole, in the preferred form, though total parallelism is not compelled.
It will be apparent from a consideration of FIGS. 1 through 4 that the problems of the prior art, in which it was impossible to provide a proper skiing configuration and a proper walking configuration in the same boot have been overcome by the present invention in which the boot permits the user to both walk and ski with his legs in the proper position for each of these differing activities.
Referring to FIG. 5, the sole of this boot is divided, for convenience of discussion, into six different portions. The first portion is designated generally at 110, in FIG. 5, the second at 120, the third at 130, the fourth at 140, these being the major functional configurations of this invention. In addition, a cleat portion 150 in the front, a cleat portion 160 in the back, and a soft bumper portion 170 on the corner of the heel portion, are provided.
Referring to FIG. 6, the ski boot of this invention is adapted to be used with a traditional ski 200 with a toe block and also includes a heel block 220 which, preferably, includes a wedge portion 222 which fits under the third portion 130 of the sole of the boot. In addition, of course, ski bindings will be provided, but these are not shown for clarity of illustration and because they constitute no part of the present invention, conventional ski bindings being quite suitable for the present invention.
Reference is now made to FIG. 7 which shows the present invention, in cross-section, in somewhat greater detail.
The first portion, indicated at 110, is usually generally flat and is adapted to rest directly upon the top of the ski. The first segment 110 lies under the metatarsal head of the user. It is in this area that the weight of the user is concentrated during skiing, although by use of the block 222, the weight of the user may be spread along substantially the full length of the foot. In either event, of course, the weight of the user is also supported at the toe and the heel by the blocks 210 and 220, as previously discussed. The first portion provides control of the ski by the user in cooperation and interaction with the bindings and the toe and heel support blocks.
Extending forwardly of the first portion is the second portion 120 of the sole, i.e., that portion formed on the sole extension which carries the weight of the user as the user is walking forward and transferring weight to the other foot during normal ambulation. The second portion slopes in an arcuate configuration medially of the user's foot and forwardly from the first portion, i.e., in a double-curved surface, or double arcuate surface now being curved or arcuate forwardly and, as best shown in FIG. 5, and is curved or arcuate medially as best shown in FIGS. 5 and 10. The second portion 120 intersects with the first portion 110 at a point below the metatarsal head and, preferably, just forward of the metatarsal head of the user's foot and continues to the forward end of the toe of the user, or slightly beyond.
The third, or resting surface portion of the boot 130 is in a generally flat configuration sloping rearwardly from the first portion upwardly toward the heel of the upper body at least to a point approximately under the medial malleolus of the user's ankle. It is upon this portion that the user stands while not skiing, i.e. on the floor during use.
The fourth portion 140 slopes in an arcuate or curved configuration laterally of the user's foot and also in a curved or arcuate configuration rearwardly of the user's foot from the third portion toward the real of the upper such that, in use, the fourth portion normally strikes the floor first when the user is walking. The four portions of the bottom form a continuous surface constructed and configured such that the user's foot rolls, first medially from the point of striking, on the fourth portion 140 to the third portion 130 and then generally centrally along the third and first portions 130 and 110 and then rolls medially on the second portion 120 as the user walks.
The rear most end of the third portion lies, in the preferred embodiment, approximately one-half the distance from the tip of the user's heel to a point lying directly between the medial malleolus of the user's ankle, i.e., about one-half the distance from the tip of the user's heel to the central line.
The front most end of the first portion lies anteriorially of a point directly beneath the metartarsal head of the user's foot, when in use.
The first portion and the third portion are generally planer forming an angle A, see FIG. 4, between the planes of the first and third portions. Angle A is generally from about five degrees to about fifteen degrees, usually about ten degrees. This angle A may, however, be as high as about thirty degrees for certain professional skiers who desire a greater bend in the knee during skiing.
Angle B is defined by a plane approximating the sole of the user's foot and a line drawn from the rear most tip of the ski boot sole to the point at which, during walking by the user, the sole by the contacts the floor and the rear tip of the boot, see FIG. 3. This angle B is generally about 30 degrees plus or minus about 8-10 degrees. While this angle is relatively critical, some reasonable variation is permitted. In a preferred embodiment, the angle B is about 30 degrees.
Reference is made to FIGS. 8, 9 and 10, respectively, which show the principal structures which have been described. FIG. 8 depicts the double curve fourth portion 140 and the resting portion 130. FIG. 9 depicts the first portion 110, which is used to support the ski boot on the ski, and, in phantom line, the curve at the forward end of the body defined by the portion 120, this curve being shown also in FIG. 10.
FIG. 5 is a view of the bottom of the sole of this invention. showing the line 300 traversed by the vector point during normal ambulation. The strike point 300A is on the lateral side of the user's foot and, of course, the force is initially concentrated at that point. As the user walks, the vector point moves forwarding and, because of the curvature, moves medially toward the center of the sole extension block where it follows along about the center during the middle part of the stride. As the stride begins to leave the middle part of the foot, anterior of the metatarsal head, the vector point moves further medially and eventually terminates at a point 300B on the medial side of the foot, just under the big toe of the user.
This rather complex configuration of the sole has a number of very significant advantages. It permits less strenuous walkiing because the line traversed by the vector point during walking is shorter, traversing from a point well inside the heel of the user to a point posterially to the tip of the toe of the user. Thus, it takes a great deal less energy and it is very much less tiring.
The natural rotation of the hip during normal ambulation is compensated for by the design of the sole extension of this invention, making walking safer, more stable, and less tiring, with less stress upon the body structures.
The ankle torques are decreased to about one-third the normal ambulatory values one would otherwise experience, and the user is more quickly brought to rest upon the third or resting portion of the sole giving better footing and more stability.
The forces exerted on the calf of the leg are relieved during standing, as well as during walking, and the user is permitted to walk with a longer and more natural gait then would otherwise be possible. The anterior muscles of the leg are thus relieved during skiing due to the decreased dorsisflexion of the ankle.
Only modest adjustment of ski binding is necessary to permit attachment of the boot to the ski and, during skiing, the user has great control which can be increased, if desired, by simply adding a wedge-shape block under the resting portion of the sole extension.
These and the general advantages of a more relaxing, comfortable walking, coupled with ease of attachment and release from the skiis, make the prsent invention a very significant advance in the art.
It will be recognized that within the concept, principles, and approaches taught by this invention, considerable variation may be introduced without departing from the scope of the invention.
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A ski boot having a curved bottom which includes four portions defining, during walking, a unique path for the force vector of the user's weight as the user walks and having defined angular and special relationships which make walking in a ski boot easier, safer and move convenient is described.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electromagnetic cutting apparatus for use with sewing machines, and in particular with flatbed sewing machines.
2. Description of the Prior Art
Applicant's Canadian Pat. No. 932,650, issued Aug. 28, 1973 discloses an electromagnetic cutting apparatus for cutting a strip of binding tape sewed onto shoe upper components. The cutting apparatus includes an electromagnetically operated plunger with a blade on the outer end thereof for cutting the tape at the leading and trailing edges of each component. The edges of the components in the vicinity of the tape are detected by means of photosensors mounted in the work surface of the apparatus. As the components and tape pass over the work surface, they occlude or open the photosensors to light from a light source mounted above such work surface. The photosensors form part of a control circuit for actuating the plunger to perform a cutting action.
The apparatus described in the above-identified Canadian patent is intended to facilitate automatic rapid and accurate cutting of a binding tape between a plurality of components fed from a sewing machine. The apparatus does, in fact, perform in the intended manner. A drawback of such apparatus is that it utilizes an impact cutting action in which the strip to be cut is guillotined by a blade driven against a hard metal insert in an anvil over which the strip is passed. With a flatbed sewing machine, there is insufficient space for such an anvil and insert arrangement. Moreover, impact cutting using the apparatus described in the above-mentioned Canadian patent is noisy, and considerable force is required for driving the blade through the material forming the strip in order to effect a clean cut.
With a view to reducing the force required to cut the strip of material, and, to a lesser extent, in order to provide a more compact, quieter sewing-cutting system, the inventor has devised a modified cutting apparatus for use with flatbed sewing machines which is connected directly to a slightly modified sewing machine and still performs the desired cutting action in a non-impacting manner and at least as quickly as the patented apparatus.
SUMMARY OF THE INVENTION
The cutting apparatus of the present invention is designed to cut a strip of material connected to a shoe or other component and extending beyond at least one edge thereof, the cutting being performed at such one edge. The apparatus includes blade means for cutting the strip; tension means for tensioning the strip during cutting thereof; first plunger means engaging the tension means; second plunger means engaging the blade means; electromagnetic drive means for moving the first plunger means and tension means from a rest position to a tensioning position on each side of the blade means, and for moving said second plunger means and blade means from a rest position to a cutting position between the tension means; sensor means for actuating said drive means when the component and strip are properly located beneath the blade means; and means for returning the first and second plunger means to the rest position.
More specifically, the tension means takes the form of two presser feet for temporarily holding the strip of material and/or component against the work surface of the sewing machine. Thus, the area of the strip between the presser feet is tensioned for cutting, which occurs when the blade passes through the strip into a slot in the sewing table. With this arrangement, there is no impact on cutting, and the forces required to effect tensioning and cutting are much less than that required for impact cutting.
The apparatus of the present invention is normally installed in a dual needle sewing machine of the type which forms part of a tandem sewing machine system. Minor modifications are made to the feed dog and presser foot of the sewing machine, and a slot for receiving the blade is provided in the throat plate of the machine.
Thus, the resulting combination of sewing and cutting elements is somewhat more compact than a system in which the sewing machine and cutting apparatus are completely separate.
The sensor means used in the apparatus of the present invention is similar to that employed in the device of the above-mentioned Canadian Pat. No. 932,650. However, in the present case, the light source is an infrared source.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of one side of the head of a sewing machine incorporating the apparatus of the present invention;
FIG. 2 is an exploded perspective view of elements used to mount the apparatus of FIG. 1 on a sewing machine;
FIG. 3 is a partly sectioned elevation view of the apparatus and sewing machine of FIG. 1;
FIG. 4 is a bottom view of the elements of FIG. 2;
FIG. 5 is a longitudinal sectional view taken generally along line V--V of FIG. 3;
FIG. 6 is a plan view of the apparatus of FIGS. 1 to 5;
FIG. 7 is a bottom view of the apparatus of FIG. 6;
FIG. 8 is an enlarged elevation view of the blade portion of the apparatus of FIG. 7; and
FIG. 9 is a block diagram of a control circuit for use in the apparatus of FIGS. 1 to 8.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings and in particular to FIGS. 1 to 3, the preferred form of cutting apparatus includes a casing 1 adjustably mounted on head end 2 of a flatbed sewing machine 3.
In order to mount the casing 1 on the sewing machine 3, the end piece (not shown) of the sewing machine is replaced with a rectangular back plate 5, which is provided with top and central outwardly extending flanges 8 and 9, respectively from receiving a smaller front plate 10. The front plate 10 (FIG. 2) is provided with enlarged, generally elliptical openings 11 through which pass screws 13 for securing the front plate to the back plate 6. The englarged openings 11 permit adjustment of the position of the front plate 10 in the direction of arrow A. A clevis-like bracket in the form of a pair of outwardly extending parallel flanges 15 is provided on the outer surface of the front plate 10 for receiving an arm 16 extending outwardly from the casing 1. The arm 16 is secured between the flanges 15 by screws 18 extending through enlarged openings 20 in the arm, whereby arm 16 and the casing 1 can be moved vertically.
A vertical bar 21 is welded to one side of the back plate 5, and supports one half of a bracket generally indicated at 23 (FIG. 1) for supporting the lower end of the casing 1. The bracket 23 includes two generally C-shaped portions 24 and 25, one of which is connected to the bar 21 and the other of which is connected to the first portion 24 by screws 27. By loosening the screws 27, the vertical position of the casing 1 and its associated elements can be adjusted. The portions 24 and 25 of the bracket 23 define a rectangular opening 29 having inclined front and rear surfaces 30 and 31, respectively permitting passage of the movable lower portion of the cutting device.
The casing 1 (FIGS. 5 to 7) includes a top portion 35, a middle portion 37 and a bottom portion 38. The top portion 35 is provided with a peripheral flange 40 for receiving bolts 41 interconnecting the top and middle portions of the casing. The top portion 35 is hollow with a closed, frusto-conical upper end 42 and an internal shoulder 43. A hollow sleeve 45 with a closed upper end 46 and a peripheral flange 47 is mounted in the casing between the top and middle portions 35 and 37, respectively. The flat periphery of the upper end 46 of the sleeve 45 and the shoulder 43 of the top portion 35 define an annular recess for a coil 48, which forms part of an electromagnetic circuit to be described in detail hereinafter. The centre of the upper end 46 of the sleeve 45 is provided with a passage 50, in which a plunger 52 is slidably mounted. The area 53 of the upper end 46 of the sleeve 45 is frusto-conical for mating with a frusto-conical recess 55 in the bottom end of a cap 56 on the upper end of the plunger 52. The cap 56 is retained in position on the plunger 52 by a nut 58 on the threaded upper end of the plunger.
The bottom surface of the upper end 46 of the sleeve 45 is provided with an annular pad 60 formed of a resilient material which acts as a stop for limiting upward movement of a disc 62, which forms the lower end of the plunger 52.
The middle portion 37 of the casing is somewhat similar in shape to the top portion 35 and the sleeve 45, including a closed upper end 63 with a central passage 65 for receiving a second plunger 67, which could be integral with the plunger 52. An annular pad 68 on the upper end 63 of the middle portion 37 around the passage 65 acts as a stop and shock absorber for the disc 62 at the lower limit of its vertical travel. The passage 65 is stepped with a large diameter upper end 70, a medium diameter middle 71 and a small diameter bottom end 73. A step at the bottom of the upper end 70 of the passage 65 is provided with an annular pad 76, which acts as a shock absorber and stop for a nut 77 on the threaded upper end of the plunger 67. A helical spring 79 around the plunger 67 extends between the bottom of the nut 77 and a shoulder 80 at the bottom of the middle 71 of the passage 65.
As in the case of the top and middle portions of the casing 1, the middle and bottom portions 37 and 38, respectively overlap, with an upper end 82 of the bottom portion 38 extending into the middle portion 37. An annular shoulder 83 in the middle portion 37 and the outer, upper end 84 of the bottom portion 38 define an annular recess for a large diameter coil 85, which also forms part of the electromagnetic circuit described in detail hereinafter. The bottom portion 38 of the casing is provided with three passages, including a rectangular central passage 87 through which passes the plunger 67, and a cylindrical passage 88 on each side thereof for a plunger 90. Each passage 88 is stepped near its top end for supporting the bottom end of a helical spring 91 around the plunger 90 and extending upwardly to the upper, inner end of a cap 92 mounted on the top of the plunger 90. The reduced diameter top end of each plunger 90 extends through the otherwise closed top of the cap 92 and is threaded for receiving a nut 93 which holds the cap in place.
Each plunger 90 is provided with a rectangular flange 95 near its bottom end for limiting upward movement of the plunger into the casing 1, which is also rectangular at its bottom end. A presser foot 96 of rectangular cross-section is secured on the bottom end of each plunger 90 by a bolt 97 and extends downwardly along one side of the plunger 67. Each presser foot 96 includes a hollow, substantially square top end, which fits onto the plunger 90, and a rectangular projection 98. The projections 98 of the presser feet define a narrow passage 99 for a blade 100 mounted on the bottom end of the plunger 67. In order to permit easy replacement of the blade 100, the bottom end of the plunger 67 is provided with a keyhole-shaped slot 101 (FIG. 8) for receiving the similarly shaped upper end 102 of the blade. Thus, when the blade 100 requires changing, one of the bolts 97 is removed so that one presser foot 96 can be removed, providing ready access to the blade 100.
It should be noted that while both plungers 90 and presser feet 96 are operated by a single coil 85, the plunger and presser foot on one side of the blade plunger 67 are independent of the plunger and presser foot on the other side of the plunger 67. This feature of the apparatus is important, since, when cutting a strip of material at the edge of a component, it is normal for one presser foot to bear on two thicknesses of material, i.e., a tape and shoe upper component while the other presser foot bears on only one thickness of material, i.e., the tape. It will also be noted (FIGS. 5 and 7) that the plunger 67 is circular in cross-sectional configuration at its top end and rectangular throughout most of the rest of its length for sliding between the presser feet 96.
A throat plate 105 is located beneath the blade 100 in the work surface of the sewing machine. A rectangular throat plate comes with the sewing machine, but a modified throat plate is prepared for the apparatus of the present invention. The modified throat plate 105 includes a slot 106 extending perpendicular to the path of travel (arrow B in FIG. 1) of the tape and shoe components. The end of the throat plate 105 in the area of the slot 106 is widened, since a wide slot in a narrow plate weakens the plate. A pair of photosensors (not shown) are provided beneath the throat plate 105 for detecting the leading and trailing edge of the component and actuating the plungers 52 and 70. Small (approximately 0.02") holes 108 and 109 are provided in the throat plate 105 permitting the passage of infrared light from a source (not shown) above the table through fibres which are glass or plastic to the photosensors located beneath the table. The holes 108 and 109 are located in the path of travel of the tape and component. With this arrangement, the photosensors can be located beneath the sewing table at a position which does not interfere with the parts of the sewing machine, e.g., the feed dog normally located beneath the throat plate 105.
The operation of the apparatus of FIGS. 1 to 8 will now be described with reference to FIG. 9. It should be noted that the caps 56 and 92 on the plungers 52 and 90 are formed of a magnetic material such as iron, and thus act as cores of solenoids 110 and 111 (FIG. 9) which include the coils 48 and 85.
The control circuit incorporating the solenoids 110 and 111 includes two photosensors 113 and 114 (referred to hereinbefore, but not shown in FIGS. 1 to 8) which are connected to signal conditioners 115 and 116, timers 117 and 118, and power impulse systems 120, 121, 122 and 123. The energy of such power impulse systems is discharged to the solenoids 110 and 111 to actuate the plungers 52 and 90.
The holes 108 and 109 and consequently the photosensors 113 and 114 are positioned in such a manner that the photosensor 113 (hole 108) is approximately 1 mm in front of the cutting line of the blade 100, and the photosensor 114 (hole 109) is approximately 1 mm behind such cutting line. The photosensor 113 controls the first cut, i.e., the cut at the leading end of a component, and the photosensor 114 controls the second cut, which is the cut at the trailing edge of the component. The photosensor 113 is activated only when covered by the leading edge of a component, and the photosensor 114 is activated only when uncovered by the trailing edge of a component.
When the photosensor 113 is covered by the leading edge of a component, there is a positive pulse of approximately 10 milliseconds at output 125 and a negative pulse of the same duration at output 126 of the signal conditioner 115. The positive pulse activates the power impulse system 120 and thus energizes the solenoid 110 which causes the plungers 90 and presser feet 96 to descend. The presser feet 96 grip the component and tape tensioning them in preparation for a cutting action. Simultaneously, the positive pulse opens the current of a power supply 128 which energizes the solenoid 110 throughout the duration of the positive pulse or tensioning step.
The negative pulse from output 126 of the signal conditioner 115 starts the timer 117, which activates the power impulse system 121 approximately 2 milliseconds after activation of the system 120. The power impulse system 121 energizes the solenoid 111 which causes the plungers 52 and 67 and the blade 100 to descend approximately 2 milliseconds after the presser feet 96. In practical terms, as soon as the photosensor 113 is covered, the solenoid 110 is energized to tension the component and tape, i.e., clamp the component and tape at the leading and trailing ends of the slot 108, and, following a 2 milliseconds delay, the solenoid 111 is energized to effect a cutting action by blade 100.
The second tensioning and cutting actions are carried out in the same manner as the first tensioning and cutting actions, except that the second photosensor 114 is used. After the trailing edge of the component has passed the second photosensor 111, a positive pulse of 10 milliseconds duration appears at output 130 and a negative pulse of the same duration appears at output 131 of the signal conditioner 122. The function of the pulses at outputs 130 and 131 is the same as those at outputs 125 and 126.
Thus, when a tape is sewed onto a plurality of shoe upper components, rather than feeding the components and tape from the machine in sausage-like fashion, the tape is cut at the leading and trailing edges of each component a short distance from where the sewing occurs.
As mentioned hereinbefore, it will be appreciated that some modifications to commercially available sewing machines will be required in order to incorporate the apparatus of the present invention in such machines. Some of the modifications have already been disclosed. Depending on the shape of the presser foot provided with the sewing machine, it may be necessary to alter the presser foot or provide a modified presser foot which will not interfere with the apparatus described hereinbefore. Normally, the presser foot provided with the machine is equipped with a slotted attachment on its outer free end for guiding the tape to be sewed onto the shoe upper components, but, like other elements which do not form part of the present invention, the attachment has not been described in detail herein.
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A cutting apparatus for cutting a strip of tape connected to a shoe upper component and extending beyond the edges thereof includes a blade for cutting the tape and presser feet for tensioning the tape during cutting. The blade and presser feet are independently actuated by plungers, which are slidable in a casing mounted on the sewing machine used to sew the tape onto the upper component. The plungers are provided with magnetic cores, and separate coils around the cores are energized in response to signals from photosensors in the work surface of the sewing machine to effect tensioning of the tape, followed by cutting at the edge of the upper component. Springs in the casing around the plungers return the plungers to a rest position, and the tape tensioning and cutting operations are repeated at each component edge.
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BACKGROUND OF THE INVENTION
While most lawn mowers available today utilize a rotating cutting blade to cut the grass and weeds, lawn mowers that employ flexible nonmetallic filament as the cutting element have been around for about ten years. Among those known to exist in the prior art are U.S. Pat. Nos. 4,232,505; 4,250,623; and 4,452,033.
It is also known to use whirling flexible filament as a weed cutting head. Such items are known in the marketplace as "string trimmers" and are sold under such trademarks as Weedwhacker® and Weedeater® among others.
The problem with the monofilament cutting heads available today is the all too frequent breakage of the line and the need to rethread the line into the often complex head arrangement.
A preliminary search by applicant provided the following U.S. patents:
U.S. Pat. No. 4,176,508 Baumann et al.
U.S. Pat. No. 4,295,324 Frantello et al.
U.S. Pat. No. 4,781,014 Conboy et al.
U.S. Pat. No. 5,174,100 Wassenberg
None of these references, either alone or in any combination thereof, anticipate(s) the present invention, nor renders this invention obvious to one of ordinary skill in this field of endeavor.
It is an object therefore to provide a monofilament based cutting head suitable for use on both a string trimmer and for a lawn mower.
It is another object to provide a cutting head that is easy to thread for usage.
It is yet another object to provide a cutter assembly having a cutting head that employs a heavier gauge of monofilament line for the cutting material relative to the prior art.
It is a further object to provide a generally universal cutting head adapted to fit most brands of string based lawn mowers.
It is a still further object to provide a generally universal cutting head adapted to fit most brands of string trimmers.
It is a yet further object to provide a cutting head that replaces the conventional bump head of a line or string trimmer.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
The invention accordingly comprises the apparatus possessing the features properties and the relation of components which are exemplified in the following detailed disclosure and the scope of the application of which will be indicated in the appended claims.
For a fuller understanding of the nature and objects of the invention reference should be made to the following detailed description, taken in conjunction with the accompanying drawings.
SUMMARY OF THE INVENTION
The invention comprises a replacement cutting head for a string trimmer which replacement head can also be utilized as a blade assembly replacement for a power lawn mower. On a string trimmer the conventional bump head is replaced by the apparatus of this invention. The cutting head, which is conventionally attached to the drive shaft of the tools aforementioned, features a whirling disk having a plurality of heavy gauge flexible polymeric members attached thereto. These members extend outwardly due to centrifugal force upon actuation of the tool and which due to the high rotational speed of the cutting head, cut through plants of all kinds. The preferred flexible members have a diamond cross section rather than a round cross section to enhance cut capability.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a perspective view of a typical string trimmer available in the marketplace, but with the cutting head of this invention attached to the bumphead, the details of the cutting heading of which are not visible.
FIG. 2 is a top plan view of the cutter portion of a string trimmer, and the cutting head of this invention mounted therein.
FIG. 3 is a side elevational view of a string trimmer with the cutting head of this invention mounted thereto.
FIG. 4 is a rear elevational view of the cutting head portion of a string trimmer with the current invention in place.
FIG. 5 is a bottom perspective view of the cutter portion with the cutting head of this invention mounted in place.
FIG. 6 is a close-up view of the bottom plate of the cutting head of this invention.
FIG. 7 is a bottom plan view of the cutting plate of this invention with one flexible member secured into operative position.
FIG. 8 is a bottom perspective view of a powered lawn mower wherein the blade has been replaced by a cutter assembly of this invention.
FIG. 9 is a top perspective view showing the cutting head of this invention mounted directly to the drive shaft.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As seen in FIG. 1, a weed cutter 10, comprises a control section 11, mounted on the upper end of an elongated angularly disposed tube, 13. The wiring to the controls, not seen, are disposed within the elongated angular tube. The elongated angular tube is connected at its opposite, i.e., lower end to the cutter portion, 15 of the apparatus.
In FIG. 2, it is seen that tube 13, is threadedly engaged to a tube receiver 17 mounted on or within a housing which comprises a cover 19. Cover 19 serves as a safety shield to prevent both access to the cutting head and to prevent stones from flying up by deflecting them and clods of dirt as well. The motor 21 may be disposed either above or below the cover as may be desired. In FIG. 4, it is seen to be disposed below the cover and above the bumphead 23. The cutter assembly 25 comprises a cutting disk 27, also seen in FIGS. 6 and 7, to which is attached a series of flexible cutting members 29. The assembly 25 also includes a mounting bolt 31 which is seen in FIGS. 4 and 5 for disposition through central aperture 33 of the cutter disk.
It is to be noted in FIG. 4 that a conventional bumphead 23 has been retained physically connected to the drive shaft, not seen of the motor 21. It is also to be gleaned from FIG. 4 and other figures that there is no string present on the bump head shown in FIG. 4. It can be concluded therefore that the cutter assembly 25 may be conventionally connected to the drive shaft of the motor 21 as by bolting, after removal of the bumphead. Either way, the operability and operation of the cutter assembly of this invention is the same.
The invention of this application comprises a cutter assembly 25, as noted previously. Cutter assembly 25 includes a cutting disk 27, preferably of a diameter between about 4 to 6 inches, and having a plurality of sets of spaced apertures 35 at uniform spacing around the periphery of the cutting disk 27. A lawn mower cutter assembly--more about which will be discussed infra--can have four such aperture pairs, while a trimmer preferably has only two opposed pairs of apertures.
The pairs of apertures are on 0.5 inch centers from each other, and each aperture of the pair is sized in cross section to achieve a tight friction fit with the threaded through flexible member. Thus for 0.155 inch diameter flexible members, an aperture diameter of about 190/1000ths inch is suggested. The center of each aperture should be no closer than about 3/8ths inch from the edge 37 of the disk.
The cutting instrument utilized with this invention is a copolymer monofilament flexible member 29 as seen in FIG. 5. This member 29 is inserted through an aperture such as 35A or 35B through one face of the disk--usually up from the bottom face for ease of operation--then looped over the edge of the disk 37, and down through the second aperture of the pair from the top face and then outwardly directed away from the disk such that the two ends are of substantially even length. A reverse feeding of the line is also contemplated to be within the scope of the invention, and is equally as satisfactory.
In the alternative a flexible member 29 may be placed through the pair of apertures 35 and retained in place by a clip 41 that grasps the flexible member in two locations to retain the flexible member.
Reference is made to the bottom perspective view of a power lawn mower, 100 with the handle missing in FIG. 8. The mower 100 depicted here is a conventional lawn mower having a housing 101, to which four wheels are mounted on axles 102, to permit movement over the ground. The mower includes a motor 103 mounted on the top of the housing and which motor has a shaft 104 which extends down through said housing. The cutter assembly of this invention 25 is bolted or otherwise connected to said shaft as is shown in FIG. 8. A conventional exit chute 105 is seen to be the point of attachment of a collection bag not shown.
Here it is seen that the cutting disk 27 is attached in like manner to the drive shaft by a bolt 31. Operation is the same. Centrifugal force makes the individual flexible members extend outwardly during rotation of the cutting disk 27, and upon impact with upstanding grass, they cut the crass down to a lower elevation. Thus it is seen that the cutter assembly of this invention can be used with any type of vegetation for the control of growth.
The flexible member employed is preferably of a diamond cross-section and is at least about 0.155 inches in diameter. The diamond shape causes either a flat surface to impact the weed or grass or a very thin edge much like a knife to do so. The exact nature of the section of the member causing impact to any particular weed or plant will depend on the orientation of the flexible member within the pair of apertures 35. Either way, better cutting is achieved than if the flexible member were to be of a circular cross section.
The preferred copolymer material is sold by Desert Extrusions Inc. of Phoenix, Ariz. as their product designated copolymer 0.155 line. Flexible members about 20 inches in total length for this invention may be cut from long spools sold in the marketplace by this vendor.
The cutting disk or whirling disk of this invention may be made of aluminum, or a nonrusting steel, or other suitable material such as polycarbonate. The central aperture 33 may be about 3/8ths inch in diameter.
It has been mentioned that when the cutter assembly of this invention is used in a lawn mower more, namely 4 pairs of uniformly spaced apertures 35 may be employed. The reason that more aperture sets may be employed for a lawn mower than for a trimmer is due to the fact that a lawn mower has more horsepower to its engine and therefore has more capability to drive an increased number of pairs of lines under load.
In FIG. 9, the cutter assembly of this invention is shown mounted directly to the drive shaft 39, of a Ryobi™ weed cutting apparatus. That is, the bumphead 23 which is not employed with this invention has been removed.
The cutter assembly 25 here too comprises a cutting disk 27, also seen in FIGS. 6 and 7, to which is attached a series of flexible cutting members 29, not seen here. The assembly 25 as noted, also includes a mounting bolt 31, only a portion being seen, for insertion into disk aperture 33.
There are many benefits to be gained from using the cutter assembly of this invention in a weed cutter. Whereas most bumpheads for trimmers today cost retail between $19.00 and $25.00, the cutter assembly of this invention can be made to sell retail for under $12.00. The reason for the big price advantage for the apparatus of this invention is that bumpheads contain one or more springs to retain the spool of line in place. Unfortunately for gardeners, all too often these springs come out and disappear during the course of a change of line spool. This necessitates the purchase of an entire bumphead.
In contrast, there is no big spool of thin line for the instant invention, only the few flexible members easily attached to the rotating disk. The apparatus of this invention is not costly to assemble and as such can have a lower pricing structure.
Whereas the line of a bumphead is consumed in direct correlation to use of the conventional string trimmer since each time the bump head is tapped to the ground, more line is dispensed. Here each flexible member, once attached can easily last a full day without replacement, even if required to cut through weeds having a diameter of a half inch as can happen when weeds go unchecked.
As mentioned earlier, the cutter assembly of this invention can be used either directly attached to the motor of a trimmer or indirectly attached, with the bumphead retained in place. If the latter approach is employed as shown in the drawings here, the line holder when empty is not replaced, or an employ line holder can be retained within the bumphead as may be required due to the nature of the construction of any particular bump head. Thus the bumphead when present, serves only as an intermediate physically present component.
The fixed line head of this invention is relatively lighter in weight than the spool head of a standard trimmer. This reduces wear and tear on the motor and clutch of the tool. A result that arises from the lower weight of the head is that the motor can reach its maximum RPM output quicker.
Since certain changes may be made in the above described apparatus without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
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A replacement cutting head for a bump head cutter of a string trimmer which replacement head can also be utilized as a blade assembly replacement for a power lawn mower. The cutting head is conventionally attached to the drive shaft of the tool, and it features a whirling disk having a plurality of heavy gauge flexible members attached thereto. These members extend outwardly due to centrifugal force upon actuation of the tool and which due to the high rotational speed of the cutting head, cut through plants of all kinds.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to quality control sampling devices generally and more particularly to rotary samplers which include impellers driven by the material to be sampled.
2. Description of the Prior Art
Rotary samplers are known in the prior art. One example is disclosed in U.S. Pat. No. 3,690,179 to Olson. Closely related devices exist in the feed, seed and grain industry and are known as grain tollers. Some examples are disclosed in the following U.S. Pat. Nos. 87,176 to Klinkerman, 198,059 to Vitt and 214,734 to Waugh. While all these references disclose means for taking portions or samples of a large mass of materials, none disclose a sample taking impeller driven by the material to be sampled.
SUMMARY OF THE INVENTION
The invention provides a rotary sampler which may be used with liquids, slurrys or particulate material, or for any matter taking the form of a falling stream. The illustrated embodiment is for sampling of seeds and grains.
A principal object of the invention is to provide a device for taking accurate samples of material from a falling stream.
A further object of the invention is to provide a sampler having a rotary impeller driven by the force of the stream of material to be sampled.
A further object is to provide a sampler which may be adjusted to sample with references to the volume or weight of the material or the velocity of the material stream.
A further object of the invention is to provide a sampler which will sample at pre set time intervals or will respond to a combination of changing parameters.
Other objects and advantages will be apparent to those skilled in the art with reference to the accompanying drawings and specifications.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the invention partially broken away to show the details of internal construction.
FIG. 2 is a plan view of the device partially broken away to show the relation of the impeller blades and the collector blade.
FIG. 3 is a sectional view taken along line 3--3 of FIG. 2.
DETAILED DESCRIPTION
Referring now to the drawing, FIG. 1 discloses a body (1) having a materials entry port (3) and an exit port (5). Written body (1) is an impeller (7) having blades (9) which are angularly adjustable and attached with nuts (11). The impeller (7) defines a hollow sample collector tube (13) upon which is mounted a hollow upward opening collector chute (15) which communicates with the inside of tube (13) via opening (17).
Impeller (7) and sample collector tube (13) which carries collector chute (15) rotates on shaft (19), which includes an adjustable shaft brake (21). Shaft (19) is supported by bearings (23) and (25) which are mounted on the frame (27).
A fixed sample exit tube (29) is attached to the lower end of frame (27) and to housing (1). The exit tube (29) is designed to receive and surround collector tube (13) at its lower end and direct the sample into a suitable receptical (not shown).
A collar (31) is mounted on tube (13) and surrounds the upper end of exit tube (29) to protect against entry of extraneous material from within housing (1).
The apparatus includes control means for regulating the frequency of sample taking. These means are described as follows: Mounted on frame (27) is a control solenoid (33) having a moving member (35) which intrudes into housing (1) and contacts a stop (37) mounted on impeller (7). A control circuit includes control (39) having a manual and an automatic mode and sensors (41) and (43) is shown schematically.
OPERATION
A stream of falling matter enters the port (3) and impinges on impeller blades (9) within housing (1). The stream then exits through port (5). When it is desired to take a sample, the solenoid (33) is energized, retracting member (35) out of contact with stop (37).
The falling stream impinging on blades (9) immediately causes the impeller (7) to rotate. This action moves the hollow collector chute (15) progressively through the falling stream of matter entering through port (3) and collect a sample thereof. The sample from the stream will enter the hollow chute (15) and move through opening (17) into the inside of collector tube (13) where it is directed into sample exit tube (29) and on to the sample receptical (not shown). After the collector chute (15) passes completely through the falling stream of material, the solenoid (33) is de-energized and moving member (35) moves down into the path of stop (37) so that further rotation of impeller (7) is prevented.
If control (39) is set for a pre-determined time interval the above described cycle will be repeated at the selected intervals. Alternately this cycle can be initiated through activation of the manual mode of control (39). Sensor (41) is intended to represent means for sensing the rate of flow into housing (1). Sensor (43) is intended to represent a device for sensing the weight of the sample or alternately the volume. Using sensors (41) and (43) alone or in combination and with other sensors control (39) can energize solenoid (35) in a variety of ways to initiate rotation of impeller (7) for sample collections.
As can be seen from FIGS. 1 and 2 blades (9) are mounted at an angle relative to the longitudinal axis of shaft (19). This angle can be varied by loosening nuts (11), readjusting blades (9) and retightning nuts (11). The speed of rotation can be varied by varying the number of blades as well. Shaft brake 21 can also be adjusted to control the speed of rotation.
It will be readily apparent to those skilled in this art that, with little change, this invention will work equally with liquids, slurrys or particulate matter. It will also be apparent that the sampler will function and take sampler entirely without housing (1). All that is necessary is that the impeller (7) with chute (15) move progressively through the moving stream of matter to be sampled. Furthermore, with little or no modification the apparatus could be used simply to continuously separate a distinct portion of material from a greater stream. Through adjustment of this angle and number of blades and collector chutes on the impeller, the device could be made to accurately separate out a fixed percentage of the main stream of material. Therefore, many modifications and changes can be made without departing from the true spirit and scope of the invention. I claim as my invention all such modifications and changes as fall within the scope and equivalence of the appended claims.
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A rotary sampler for taking quality control samples from a falling stream of material is disclosed. The sampler includes an impeller which is driven by the falling material. As the impeller turns a hollow collector blade moves through the falling stream. Material within the stream is diverted through the hollow collector blade to a central collector tube. The device includes means for controlling the frequency of sampling.
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FIELD OF THE INVENTION
The present invention relates generally to deadbolt assemblies and particularly to an extendable deadbolt, which can extend from one standard size to another, a deadbolt assembly having a pivotable faceplate and a deadbolt assembly suitable for use with doors of varying thickness.
BACKGROUND OF THE INVENTION
Many kinds of deadbolt assemblies are commercially available. Deadbolts are thrown and retracted by means of a key-operated cylinder which passes through a hub of the deadbolt assembly. Turning the key turns the hub, which causes a cam or actuator to throw or retract the bolt. Some deadbolts are operated by a single cylinder, wherein the deadbolt is actuated by a key from outside the door and by a turnpiece from inside the door. Other deadbolts are operated by a double cylinder, wherein the deadbolt is thrown or retracted by a key from both sides of the door.
Deadbolts are thrown and retracted into a doorpost through a metal plate called a strike. The distance between the strike and the center of the hub is called the backset. In the United States, standard backsets are generally 2.375 inches or 2.75 inches. The throw of the deadbolt varies from one lock to another, with the maximum generally being 1 inch.
Most deadbolts are fixed at one standard backset or another. However, deadbolts with an adjustable backset are known. For example, KWIKSET manufactures and sells a deadbolt with a helical screw body (for example, its 880 series). By turning the strike, one can change the backset from 2.375 to 2.75 inches, and vice versa. SCHLAGE manufactures a line of deadbolts (B160 Grade 3 deadbolts) wherein the hub can be slid from one end of an elliptical hole to another, thereby adjusting the backset from one standard size to another.
However, adjustable-backset deadbolts of the art suffer from a drawback of a relatively weak mechanical connection between the deadbolt and the hub end of the assembly. This makes adjustable-backset deadbolts generally unsuitable for high security installations. In addition, the spacing between mounting screws used to mount the key-operated cylinder to the deadbolt assembly are not standard in prior art adjustable-backset assemblies.
Generally, deadbolt assemblies are not particularly flexible when non standard applications are required. For example, when conventional deadbolt assemblies are mounted on bevel-mounted doors, the faceplates must be specially enlarged and specially aligned to match the particular application. Similarly, when conventional deadbolt assemblies are mounted on doors of non-standard thickness, special hardware must be used.
SUMMARY OF THE INVENTION
The present invention seeks to provide a novel deadbolt with an adjustable backset wherein there is a positive and strong mechanical link at all times between the deadbolt and the hub end of the deadbolt assembly. The deadbolt itself extends all the way to a mounting screw used to mount the key-operated cylinder to the deadbolt assembly. This is in contrast to prior art deadbolt assemblies which have shorter deadbolts. The longer deadbolt provides added strength against break-in attempts. Moreover, in the present invention, unlike the prior art, the spacing between mounting screws used to mount the key-operated cylinder to the deadbolt assembly is standard.
There is thus provided in accordance with a preferred embodiment of the present invention an adjustable deadbolt assembly including a deadbolt, a cylinder-connecting portion formed with mounting provisions for mounting thereto a lock cylinder, an actuator formed with a hub connectable to a lock cylinder, the hub being journaled in the cylinder-connecting portion, and a link bar that connects the actuator to the deadbolt at at least one of a plurality of attachment points formed on at least one of the deadbolt and the link bar. The attachment points may be notches formed on a periphery of the deadbolt or on the link bar.
In accordance with a preferred embodiment of the present invention the deadbolt is slidingly disposed in a tube, and the cylinder-connecting portion, the link bar, the actuator and the deadbolt are selectively removable from the tube.
Further in accordance with a preferred embodiment of the present invention a pin is placed between the tube and the cylinder-connecting portion, the pin being pushable inwards into a hole formed in the cylinder-connecting portion so as to release the tube from the cylinder-connecting portion, thereby permitting withdrawing the cylinder-connecting portion, the actuator, the link bar and the deadbolt from the tube.
Still further in accordance with a preferred embodiment of the present invention the deadbolt has a length such that the deadbolt extends to one of the mounting provisions when the link bar fits into one of the notches formed on the deadbolt.
Additionally in accordance with a preferred embodiment of the present invention the mounting provisions are mounting holes spaced from one another corresponding to a spacing between mounting screws of a lock cylinder.
In accordance with a preferred embodiment of the present invention a strike is attached to the tube wherein a distance, called a backset, between an outer surface of the strike and a center of the hub is defined by the notch in which the link bar is fitted. Preferably the backset varies from about 2.375 inches to about 2.75 inches.
There is also provided in accordance with a preferred embodiment of the present invention a method for adjusting an adjustable deadbolt assembly including withdrawing the cylinder-connecting portion, the link bar, the actuator and the deadbolt from the tube, moving the link bar from one attachment point to another, and sliding the cylinder-connecting portion, the link bar, the actuator and the deadbolt back into the tube.
There is also provided in accordance with a preferred embodiment of the present invention a deadbolt assembly including a deadbolt, a tube in which the deadbolt is slidingly disposed including an end through which said deadbolt emerges when extended, and a faceplate pivotably connected to an end of the tube. The deadbolt assembly may be but need not necessarily be an adjustable deadbolt assembly of the type described hereinabove.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawings in which:
FIGS. 1 and 2 are simplified exploded and pictorial illustrations, respectively, of an adjustable deadbolt assembly constructed and operative in accordance with a preferred embodiment of the present invention;
FIG. 3 is a simplified pictorial illustration of a deadbolt in a tube, which forms part of the adjustable deadbolt assembly of FIGS. 1 and 2 ;
FIGS. 4 and 5 are simplified pictorial illustrations of the deadbolt and an actuator in respective relatively short and relatively long backset positions;
FIGS. 6 and 7 are simplified sectional illustrations of the relatively short backset position shown in FIG. 4 , wherein FIG. 6 is taken along lines VI—VI in FIG. 4 and FIG. 7 is taken along lines VII—VII in FIG. 6 ;
FIGS. 8 and 9 are simplified sectional illustrations of the relatively long backset position shown in FIG. 5 , wherein FIG. 8 is taken along lines VIII—VIII in FIG. 5 and FIG. 9 is taken along lines IX—IX in FIG. 8 ;
FIG. 10 is a simplified pictorial illustration of a deadbolt assembly having a pivotably mounted faceplate in accordance with a preferred embodiment of the present invention and illustrating three different orientations of the faceplate;
FIG. 11 is an exploded view of part of the deadbolt assembly of FIG. 10 , showing a preferred embodiment of pivotably mounted faceplate; and
FIG. 12 is an assembled view of the part of the deadbolt assembly shown in FIG. 11 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Reference is now made to FIGS. 1-9 which illustrate an adjustable deadbolt assembly 10 constructed and operative in accordance with a preferred embodiment of the present invention.
Deadbolt assembly 10 preferably includes a deadbolt 12 formed with a plurality of notches 14 on a periphery thereof. Two such notches 14 are shown in the illustrated embodiment ( FIGS. 4-6 and 8 ), but it is appreciated that the invention is not limited to this number of notches. Assembly 10 also preferably includes a cylinder-connecting portion 16 formed with mounting provisions 18 for mounting thereto a lock cylinder 20 . Lock cylinder 20 is shown as a double cylinder, wherein deadbolt 12 is thrown or retracted by a key (not shown) from both sides of a door (not shown). However, it is appreciated that other arrangements, such as a single cylinder, may also be used.
Mounting provisions 18 are preferably mounting holes 17 and 19 ( FIGS. 3-5 ) which are spaced from one another corresponding to a spacing between mounting screws 21 of lock cylinder 20 (FIG. 1 ). It is noted that in the illustrated embodiment, mounting hole 17 is formed as a half hole, and deadbolt 12 is preferably formed with a half hole 15 . As described hereinbelow with reference to FIG. 6 , when deadbolt 12 is placed in a short backset position, half holes 15 and 17 form a complete hole.
An actuator 22 is preferably formed with a hub 24 into which lock cylinder 20 is connected, as is known in the art. Hub 24 is preferably journaled in cylinder-connecting portion 16 . Cylinder-connecting portion 16 may be formed of two halves 16 A and 16 B, secured by a fastener such as a retaining clip 26 , for example (FIGS. 7 and 9 ). A link bar 28 preferably connects actuator 22 to deadbolt 12 . Link bar 28 is preferably formed with an aperture 30 in which is received a portion of actuator 22 , such as a tongue 32 . An end 34 of link bar 28 is preferably adapted to fit into one of notches 14 formed on deadbolt 12 . Alternatively, as shown in dotted lines in FIG. 4 , notches 14 may be formed on link bar 28 and deadbolt 12 may be formed with protrusions 33 which are received in one of the notches formed on link bar 28 . In general, link bar 28 connects actuator 22 to deadbolt 12 at one of a plurality of attachment points formed on either deadbolt 12 or link bar 28 .
Deadbolt 12 is preferably disposed in a tube 36 . Tube 36 is preferably connected to the rest of assembly 10 by means of a pin 38 , which is preferably spring-loaded by a spring 40 . A strike 42 is preferably attached to tube 36 . The distance (backset) between an outer surface of strike 42 and a center of hub 24 is defined by the notch 14 in which link bar 28 is fitted.
In order to change the backset of deadbolt assembly 10 , pin 38 is pushed inwards (against spring 40 ) into a hole 44 ( FIGS. 4 and 5 ) formed in cylinder-connecting portion 16 so as to release tube 36 from cylinder-connecting portion 16 . This permits withdrawing and removing cylinder-connecting portion 16 , actuator 22 , link bar 28 and deadbolt 12 from tube 36 , generally in the direction of an arrow 46 (FIGS. 6 and 8 ). Link bar 28 may now be moved from one of notch 14 to another. If link bar 28 is fitted in the notch 14 closest to strike 42 , then the backset is relatively short ( FIGS. 4 , 6 and 7 ). Conversely, if link bar is fitted in the notch 14 furthest from strike 42 , then the backset is relatively long ( FIGS. 5 , 8 and 9 ). Afterwards, cylinder-connecting portion 16 , link bar 28 , actuator 22 and deadbolt 12 are slid back into tube 36 .
It is noted that deadbolt 12 preferably has a length such that it extends to one of mounting provisions 18 when link bar 28 is adjusted to the shorter backset, as seen best in FIG. 6 . In this position, half holes 15 and 17 form a complete hole.
In accordance with American industry standards, the backset of the present invention preferably varies from about 2.375 inches to about 2.75 inches. Of course, other dimensions are also in the scope of the invention.
Reference is now made to FIG. 10 , which is a simplified pictorial illustration of a deadbolt assembly having a pivotably mounted faceplate in accordance with a preferred embodiment of the present invention and illustrating three different orientations of the faceplate and to FIGS. 11 and 12 , which show details of the pivotable mounting of the faceplate.
As seen in FIGS. 10-12 , there is provided a deadbolt assembly 100 , which may be, but need not necessarily be, of the type described hereinabove with reference to FIGS. 1-9 . The deadbolt assembly 100 includes inter alia a tube 102 through which a bolt 103 is slidably displaceable.
In the illustrated embodiment, a forward end 104 of tube 102 is formed with a pair of oppositely disposed apertured lugs 106 and 108 having formed therein respective apertures 110 and 112 . Preferably, the lugs 106 and 108 are positioned such that when the deadbolt assembly 100 is mounted onto a door, apertures 110 and 112 lie along a vertical axis 114 .
In the illustrated embodiment, a mounting plate 120 is pivotably mounted onto tube 102 , preferably for pivotable mounting about the vertical axis 114 (FIG. 10 ). Preferably, the mounting plate 120 is formed with mounting lugs 126 and 128 having formed therein respective apertures 130 and 132 .
A retaining spring 134 having respective engagement ends 136 and 138 is arranged to pivotably retain mounting plate 120 onto tube 102 . End 136 extends through respective apertures 110 and 130 of respective lugs 106 and 126 , while end 138 extends through respective apertures 130 and 132 of respective lugs 108 and 128 , thus defining pivot axles both of which preferably extend along vertical axis 114 .
A face plate 140 , to which is attached the mounting plate 120 , is readily screwed onto an edge of a door (not shown) by means of mutually alignable screw holes 142 and 144 in the face plate which correspond to screw holes 146 and 148 in the mounting plate 120 .
It is appreciated that the arrangement of FIGS. 10-12 is particularly helpful when mounting a deadbolt assembly on a door, which is hung in a bevel arrangement and ensures that the faceplate 140 is centered relative to the deadbolt. In this way, a deadbolt aperture 150 in the faceplate 140 may be made as small as possible.
It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention includes both combinations and subcombinations of the features described hereinabove as well as modifications and variations thereof which would occur to a person of skill in the art upon reading the foregoing description and which are not in the prior art.
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An adjustable deadbolt assembly including a deadbolt, a cylinder-connecting portion formed with mounting provisions for mounting thereto, a lock cylinder, an actuator formed with a hub connectable to a lock cylinder, the hub being journaled in the cylinder-connecting portion and a link bar that connects the actuator to the deadbolt at at least one of a plurality of attachment points formed on at least one of the deadbolt and the link bar. A method for adjusting an adjustable deadbolt assembly is also disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority from Japanese Patent Application No. 2011-35117 filed on Feb. 21, 2011, the entire contents of which are incorporated herein by reference.
BACKGROUND
[0002] 1. Field
[0003] The embodiments discussed herein relate to a semiconductor device and a method for manufacturing the semiconductor device.
[0004] 2. Description of Related Art
[0005] Materials including GaN, AlN, InN, and a mixed crystal of these materials, which are included in nitride semiconductors, have a wide band-gap and are used in high-output electronic devices, short-wavelength light-emitting devices, and the like. Field-effect transistors (FETs), for example, high electron mobility transistors (HEMTs) are used in high-output-high-efficiency-amplifiers or high-power switching devices, and the like. In an HEMT including an electron supply layer having AlGaN and an electron transit layer having GaN, strain due to a difference in a lattice constant between AlGaN and GaN may occur in AlGaN and piezoelectric polarization may occur. Since a high-concentration two-dimensional electron gas is generated by the piezoelectric polarization, a high-output device may be provided.
[0006] For example, related are is disclosed in Japanese Laid-open Patent Publication Nos. 2002-359256, 2007-19309, and 2009-76845.
SUMMARY
[0007] According to one aspect of the embodiments, a semiconductor device includes: a semiconductor layer disposed above a substrate; an insulating film formed by oxidizing a portion of the semiconductor layer; and an electrode disposed on the insulating film, wherein the insulating film includes gallium oxide, or gallium oxide and indium oxide.
[0008] Additional advantages and novel features of the invention will be set forth in part in the description that follows, and in part will become more apparent to those skilled in the art upon examination of the following or upon learning by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 illustrates an exemplary semiconductor device;
[0010] FIGS. 2A to 2I illustrate an exemplary method for producing a semiconductor device;
[0011] FIG. 3 illustrates an exemplary a characteristic of supercritical water;
[0012] FIG. 4 illustrates an exemplary a semiconductor device;
[0013] FIG. 5 illustrates an exemplary a discrete-packaged semiconductor device;
[0014] FIG. 6 illustrates an exemplary power supply device; and
[0015] FIG. 7 illustrates an exemplary a high-frequency amplifier.
DESCRIPTION OF EMBODIMENTS
[0016] In an HEMT which is used in a high-output-high-efficiency-amplifier, a high-power switching device, or the like, normally-off may be applied thereto, and the HEMT may have a high breakdown voltage. In order to achieve a normally-off operation, a portion of a semiconductor layer located under a gate electrode is removed to form a gate recess. In a gate recess structure, the threshold voltage becomes positive without increasing the resistance between electrodes. In order to obtain a high drain breakdown voltage and a high gate breakdown voltage, a metal insulator semiconductor (MIS) structure including a gate insulating film is used in an FET or HEMT having a lateral structure. The gate recess structure and the MIS structure may be applied to an HEMT including a GaN-based semiconductor material.
[0017] In a semiconductor device having the gate recess structure and the MIS structure, a portion of a semiconductor layer formed by epitaxial growth or the like is removed by, for example, etching, and an insulating film may be formed on the etched portion. Consequently, the semiconductor device may be damaged by the etching.
[0018] In embodiments, substantially the same components and the like are assigned the same reference numerals, and the description of those components may be omitted or reduced.
[0019] FIG. 1 illustrates an exemplary semiconductor device. The semiconductor device illustrated in FIG. 1 may include a transistor called HEMT.
[0020] The semiconductor device includes a semiconductor layer including an electron transit layer 21 , a spacer layer 22 , an electron supply layer 23 , and a cap layer 24 , the semiconductor layer being provided on a buffer layer 20 formed on a substrate 10 corresponding to a semiconductor or the like. The semiconductor layer is formed by epitaxial growth such as metal-organic vapor phase epitaxy (MOVPE). A source electrode 42 and a drain electrode 43 that are coupled to the electron supply layer 23 are provided. An insulating film 30 corresponding to a gate insulating film is provided on a region of the electron transit layer 21 where a gate electrode 41 is formed. The gate electrode 41 is provided on the insulating film 30 . The source electrode 42 and the drain electrode 43 may be coupled to the electron transit layer 21 . A protective film including an insulator may be provided so as to cover the cap layer 24 .
[0021] The substrate 10 may be any one of a Si substrate, a SiC substrate, a sapphire (Al 2 O 3 ) substrate, and the like. For example, when a Si substrate is used as the substrate 10 , the buffer layer 20 may be provided. When a material other than silicon is used as the substrate 10 , the buffer layer 20 may not be provided. The electron transit layer 21 may be composed of i-GaN. The spacer layer 22 may be i-AlGaN. The electron supply layer 23 may be composed of n-AlGaN. The cap layer 24 may be an n-GaN. A two-dimensional electron gas (2DEG) 21 a is generated on the electron supply layer 23 side of the electron transit layer 21 .
[0022] The gate electrode 41 , the source electrode 42 , and the drain electrode 43 may include a metal material. The insulating film 30 corresponding to the gate insulating film is formed by oxidizing the spacer layer 22 , the electron supply layer 23 , and the cap layer 24 . For example, by oxidizing i-AlGaN corresponding to the spacer layer 22 , n-AlGaN corresponding to the electron supply layer 23 , and n-GaN corresponding to the cap layer 24 , Ga 2 O 3 and Al 2 O 3 are formed. The Ga 2 O 3 and Al 2 O 3 may correspond to the insulating film 30 . Alternatively, the electron supply layer 23 and the cap layer 24 may be oxidized. Alternatively, only the cap layer 24 may be oxidized.
[0023] The semiconductor layer may include GaN and AlGaN. Alternatively, the semiconductor layer may include a nitride semiconductor such as InAlN or InGaAlN. The insulating film 30 corresponding to the gate insulating film may be Ga 2 O 3 , In 2 O 3 , Al 2 O 3 , and the like formed by oxidizing InAlN and InGaAlN.
[0024] FIGS. 2A to 2I illustrate an exemplary a method for producing a semiconductor device.
[0025] As illustrated in FIG. 2A , a buffer layer 20 is formed on a substrate 10 . A semiconductor layer including, for example, an electron transit layer 21 , a spacer layer 22 , an electron supply layer 23 , and a cap layer 24 is formed on the buffer layer 20 by epitaxial growth such as MOVPE. A silicon nitride (SiN) film 61 for forming a mask is formed on the cap layer 24 . The substrate 10 may be a substrate composed of Si, SiC, sapphire (Al 2 O 3 ), or the like. The buffer layer 20 for epitaxially growing the electron transit layer 21 and other layers is formed on the substrate 10 . The buffer layer 20 may be, for example, an undoped i-AlN layer having a thickness of 0.1 μm. The electron transit layer 21 may be an undoped i-GaN layer having a thickness of 3 μm. The spacer layer 22 may be an undoped i-AlGaN layer having a thickness of 5 nm. The electron supply layer 23 may be an n-Al 0.25 Ga 0.75 N layer having a thickness of 30 nm. The electron supply layer 23 is doped with Si serving as an impurity element at a concentration of 5×10 18 cm −3 . The cap layer 24 may be an n-GaN layer having a thickness of 10 nm. The cap layer 24 is doped with Si serving as an impurity element at a concentration of 5×10 18 cm −3 . The silicon nitride (SiN) film 61 having a thickness of 200 nm is deposited on the cap layer 24 by plasma enhanced chemical vapor deposition (PECVD).
[0026] As illustrated in FIG. 2B , a resist pattern 62 is formed on the silicon nitride film 61 . For example, a photoresist is applied onto the silicon nitride film 61 . The photoresist is exposed by an exposure apparatus and then developed to form the resist pattern 62 . The resist pattern 62 may have an opening in a region where an insulating film corresponding to a gate insulating film is to be formed.
[0027] As illustrated in FIG. 2C , the silicon nitride film 61 in a region where the resist pattern 62 is not formed is removed by dry etching such as reactive ion etching (RIE). The resist pattern 62 may also be removed. A mask 64 including the silicon nitride film 61 having an opening 63 is formed. The silicon nitride film 61 is used as the material of the mask 64 . Alternatively, other materials that are not easily oxidized may be used.
[0028] As illustrated in FIG. 2D , the spacer layer 22 , the electron supply layer 23 , and the cap layer 24 that are exposed in the opening 63 of the mask 64 are oxidized to form an insulating film 30 corresponding to a gate insulating film. For example, the insulating film 30 may be formed by oxidizing the spacer layer 22 , the electron supply layer 23 , and the cap layer 24 using supercritical water. For example, the silicon nitride film 61 having the opening 63 is placed at a predetermined position in a chamber filled with pure water. The inside of the chamber is set to a high-temperature, high-pressure state, and the pure water in the chamber becomes supercritical water. Since supercritical water has a strong oxidizing power, materials that are oxidized at high temperatures are oxidized at lower temperatures by using supercritical water. For example, GaN and AlGaN are thermally oxidized at a temperature of 1,000° C. or higher. However, the crystal structures of the epitaxially grown semiconductor layers may be broken by heating at such a high temperature. In oxidation with supercritical water, supercritical water at a temperature of 700° C. or lower, for example, about 380° C. is used, and thus a semiconductor layer in a predetermined region that is in contact with supercritical water is oxidized. A nitride semiconductor is oxidized without causing disorder of the crystal structure of the semiconductor layer. The insulating film 30 corresponding to the gate insulating film is formed by oxidizing a part of a semiconductor layer including a nitride semiconductor without degrading characteristics of the semiconductor device.
[0029] FIG. 3 illustrates an exemplary characteristic of supercritical water. The term “supercritical water” refers to water in a state at a temperature of 374° C. or higher and a pressure of 218 atmospheres or more, and refers to, for example, water in a state where gas and liquid are not distinguished from each other. Supercritical water has properties different from those of normal water. The properties of supercritical water may accelerate a chemical reaction. By using supercritical water, GaN and AlGaN, which are oxidized at high temperatures, are oxidized at relatively low temperatures. For example, by oxidizing the spacer layer 22 corresponding to i-AlGaN, the electron supply layer 23 corresponding to n-AlGaN, or the cap layer 24 corresponding to n-GaN, the insulating film 30 corresponding to Ga 2 O 3 and Al 2 O 3 is formed. The spacer layer 22 , the electron supply layer 23 , and the cap layer 24 are oxidized by using supercritical water at a temperature of 700° C. or lower, for example, 550° C. or lower to form the insulating film 30 . Subcritical water, which is in a state at a temperature and a pressure slightly lower than those of the critical point, also has a strong oxidizing power. The oxidizing power of water in a state close to subcritical water is also relatively strong. Accordingly, GaN and AlGaN may be oxidized at low temperatures by using water that is in a liquid state at a temperature higher than 100° C., as in the case of supercritical water. For example, a semiconductor layer including a nitride semiconductor may be oxidized at a temperature equal to or lower than a temperature at which the source electrode 42 and the drain electrode 43 are brought into ohmic contact with each other.
[0030] A recess is formed in the oxidized region formed by oxidizing the spacer layer 22 , the electron supply layer 23 , and the cap layer 24 , and in addition, an insulating film is formed in the recess. A process of forming the recess and a process of forming the insulating film are performed contemporaneously, and thus the manufacturing process may be simplified.
[0031] Similarly, in a semiconductor device including a nitride semiconductor other than GaN and AlGaN, an oxidized film corresponding to an insulting film may be formed. For example, also in a semiconductor device in which a nitride semiconductor such as InAlN or InGaAlN is used as a semiconductor layer, an insulating film including In 2 O 3 , Ga 2 O 3 , and Al 2 O 3 may be formed by oxidation using supercritical water or the like.
[0032] As illustrated in FIG. 2E , the silicon nitride film 61 is removed. For example, the silicon nitride film 61 is removed by wet etching using hot phosphoric acid.
[0033] As illustrated in FIG. 2F , a resist pattern 65 is formed. For example, a photoresist is applied onto the surface of the cap layer 24 . The photoresist is exposed by an exposure apparatus and then developed to form the resist pattern 65 . The resist pattern 65 has openings in regions where a source electrode 42 and a drain electrode 43 are to be formed. Before the formation of the resist pattern 65 , an element isolation region (not illustrated) may be formed. A resist pattern (not illustrated) having an opening in the element isolation region is formed. Dry etching using a chlorine-based gas or ion implantation is conducted in the opening to form the element isolation region. The resist pattern (not illustrated) used for forming the element isolation region is removed.
[0034] As illustrated in FIG. 2G , dry etching such as RIE is conducted using a chlorine-based gas to remove the cap layer 24 in the openings of the resist pattern 65 . The resist pattern 65 is also removed by an organic solvent or the like. Thus, the cap layer 24 is removed in the regions where the source electrode 42 and the drain electrode 43 are to be formed.
[0035] As illustrated in FIG. 2H , the source electrode 42 and the drain electrode 43 are formed. For example, a resist pattern (not illustrated) having openings in the regions where the source electrode 42 and the drain electrode 43 are to be formed is formed. A photoresist is applied onto the surface on which the cap layer 24 is formed. The photoresist is exposed by an exposure apparatus and then developed to form the resist pattern. A metal film, for example, a Ta film having a thickness of about 20 nm or an Al film having a thickness of about 200 nm is formed over the entire surface by vacuum deposition or the like. The metal film deposited on the resist pattern is then removed by lift-off using an organic solvent. The metal film in regions where the resist pattern is not formed is used as the source electrode 42 and drain electrode 43 which are disposed on the electron supply layer 23 and includes Ta/Al. The metal film, which includes Ta and is in contact with the cap layer 24 , is heat-treated in a nitrogen atmosphere at a temperature in the range of 400° C. to 700° C., for example, at 550° C., thereby establishing ohmic contact between the source electrode 42 and the drain electrode 43 . In the case where the ohmic contact is established without heat treatment, the heat treatment may not be conducted.
[0036] As illustrated in FIG. 2I , a gate electrode 41 is formed. For example, a resist pattern (not illustrated) having an opening in a region where the gate electrode 41 is to be formed is formed. A photoresist is applied onto the surface on which the cap layer 24 is formed. The photoresist is exposed by an exposure apparatus and then developed to form the resist pattern. A metal film, for example, a Ni film having a thickness of about 40 nm or a Au film having a thickness of about 400 nm is formed over the entire surface by vacuum deposition. The metal film deposited on the resist pattern is then removed by lift-off using an organic solvent. The metal film in a region where the resist pattern is not formed is used as the gate electrode 41 which is disposed on the insulating film 30 and includes Ni/Au. Heat treatment or the like may then be conducted as required.
[0037] FIG. 4 illustrates an exemplary semiconductor device. As illustrated in FIG. 4 , a protective film 50 may be formed in regions where the cap layer 24 is exposed. For example, the protective film 50 may include an insulator. For example, the protective film 50 may be formed by depositing an aluminum oxide film or a silicon nitride film by plasma atomic layer deposition (ALD) or the like.
[0038] FIG. 5 illustrates an exemplary discrete-packaged semiconductor device. The semiconductor device illustrated in FIG. 1 or 4 may be discrete-packaged. FIG. 5 schematically illustrates the inside of the discrete-packaged semiconductor device. Therefore, the arrangement of electrodes etc. illustrated in FIG. 5 may be different from the structure illustrated in FIG. 1 or 4 .
[0039] For example, the semiconductor device illustrated in FIG. 1 or 4 is cut by dicing or the like to form a semiconductor chip 410 of HEMT including a GaN-based semiconductor material. The semiconductor chip 410 is fixed on a lead frame 420 with a die attaching agent 430 such as solder.
[0040] A gate electrode 441 is coupled to a gate lead 421 with a bonding wire 431 . A source electrode 442 is coupled to a source lead 422 with a bonding wire 432 . A drain electrode 443 is coupled to a drain lead 423 with a bonding wire 433 . The bonding wires 431 , 432 , and 433 may include a metal material such as Al. The gate electrode 441 may be a gate electrode pad, and is coupled to, for example, the gate electrode 41 . The source electrode 442 may be a source electrode pad, and is coupled to, for example, the source electrode 42 . The drain electrode 443 may be a drain electrode pad, and is coupled to, for example, the drain electrode 43 .
[0041] A resin seal is performed by a transfer molding method using a molding resin 440 , thus producing a semiconductor device in which the HEMT including the GaN-based semiconductor material is discrete-packaged.
[0042] FIG. 6 illustrates an exemplary power supply device. A power supply device 460 illustrated in FIG. 6 includes a high-voltage primary side circuit 461 , a low-voltage secondary side circuit 462 , and a transformer 463 provided between the primary side circuit 461 and the secondary side circuit 462 . The primary side circuit 461 includes an AC power supply 464 , for example, a bridge rectifier circuit 465 , and a plurality of switching elements, for example, four switching elements 466 and one switching element 467 , etc. The secondary side circuit 462 includes a plurality of switching elements, for example, three switching elements 468 . The semiconductor device illustrated in FIG. 1 or 4 may be used as the switching elements 466 and 467 of the primary side circuit 461 . The switching elements 466 and 467 of the primary side circuit 461 may each be a normally-off semiconductor device. The switching elements 468 of the secondary side circuit 462 may each be a metal-insulator-semiconductor field-effect transistor (MISFET) containing silicon.
[0043] FIG. 7 illustrates an exemplary high-frequency amplifier. A high-frequency amplifier 470 illustrated in FIG. 7 may be applied to a power amplifier for a base station of mobile phones. The high-frequency amplifier 470 includes a digital pre-distortion circuit 471 , mixers 472 , a power amplifier 473 , and a directional coupler 474 . The digital pre-distortion circuit 471 compensates for non-linear distortion in an input signal. One of the mixers 472 mixes the input signal in which the non-linear distortion is compensated for with an alternating current signal. The power amplifier 473 amplifies the input signal mixed with the alternating current signal. The power amplifier 473 illustrated in FIG. 7 may include the semiconductor device illustrated in FIG. 1 or 4 . The directional coupler 474 performs, for example, monitoring of an input signal and an output signal. For example, based on switching of a switch, the other mixer 472 may mix an output signal with an alternating current signal and transmit the mixed signal to the digital pre-distortion circuit 471 . Since the semiconductor device illustrated in FIG. 1 or 4 is used in the power amplifier 473 , a power supply device and an amplifier may be provided at a low cost.
[0044] Example embodiments of the present invention have now been described in accordance with the above advantages. It will be appreciated that these examples are merely illustrative of the invention. Many variations and modifications will be apparent to those skilled in the art.
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A semiconductor device includes: a semiconductor layer disposed above a substrate; an insulating film formed by oxidizing a portion of the semiconductor layer; and an electrode disposed on the insulating film, wherein the insulating film includes gallium oxide, or gallium oxide and indium oxide.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of United Kingdom Patent Application Serial No. 0606845.6, filed on Apr. 5, 2006, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to particles labelled beads incorporating reporter moieties which are useful in a variety of applications for labelling and detection purposes. The term “beads” is used for convenience and is not intended to impose any particular shape limitation. Thus, for example, the beads may be spherical but other configurations are possible.
GROUND OF THE INVENTION
[0003] Labelled beads have been used for many years in diagnostics testing, microscope-based assays, flow cytometry-based assays and combinatorial library synthesis. They also have potential to be used in a wide range of applications including biological monitoring, security/anti-counterfeiting, optical coding, biological assays, optical data storage and sensors.
[0004] A labelled bead will generally contain a plurality of reporter moieties. The reporter moieties may, for example, be fluorescent species such as fluorescent dyes or a quantum dot. (For the purposes of the present invention a single dye molecule or quantum dot is considered to be a reporter moiety). Further possibilities include the use of magnetic particles and specifically shaped particles as reporter moieties.
[0005] Labelled beads may contain different “species” of reporter moieties. Thus, for example, a labelled bead may contain two or more different types of fluorescent dye or two or more different types of quantum dot. Depending on the number of each species present, the bead will provide a particular signal which may in effect be considered to be a “bar-code”. Put another way, there will be a first signal from the first species of reporter moiety, a second signal from the second species of reporter moiety etc. In addition the intensity of the signal from the first reporter moiety may be increased or decreased by the presence of the second reporter moiety. The particular combination of signals uniquely identifies the bead.
[0006] It will of course be appreciated that labelled beads may be produced with different combinations of reporter moieties so that different types of bead are distinguished by their “barcode” signal.
[0007] By way of illustration, such beads may be used for labelling (“tagging”) proteins or nucleic acids. Thus molecules of a first type of nucleic acid or protein may be tagged (e.g. by incubation, covalent attachment, adsorption etc.) with labelled beads providing a first barcode signal. Similarly protein or nucleic acid molecules of a second type may be tagged with labelled beads providing a second barcode signal. The tagged protein or nucleic acids may then be admixed and subjected to a particular reaction. The individual barcodes allow the product mixture to be examined (e.g. after a separation procedure) to determine the origin of the tagged molecule in other words which specific reaction sequences the bead has been exposed to or else which known molecule has been attached to the bead).
[0008] Most of the bar-coded labelled particle libraries currently available have been produced by encoding beads with different concentrations of fluorescent dyes and/or metal (including magnetic metal) particles. In the case where the moieties are fluorescent dyes, the size of the library is limited by the overlapping excitation and emission spectra of the dyes. There are also limitations on libraries produced using metal particles as the reporter moieties.
[0009] Some of the above mentioned disadvantages are overcome by the use of quantum dots as the reporter moieties.
[0010] Quantum dots are a subset of nanoparticles that when excited emit light, with quantum yields of between 30-70% and narrow emission bands across the visible spectrum and extending to both the UV and near infrared spectrum. Compared with conventional fluorescent probes (e.g. organic dyes and lanthanides) quantum dots have a number of advantages. Most notably quantum dots absorb light over a wide range of wavelengths so a number of different light-emitting quantum dots can be stimulated using a single light source to produce an output in parallel, a so-called optical barcode. This is in contrast to conventional fluorescent compounds for which (i) their absorption and emission spectra are closely coupled (thus requiring a number of different light sources for multiplexing purposes), and (ii) their emission spectrum is often extremely broad and overlapping with its absorption spectra.
[0011] Labelled beads comprised of polymeric particles incorporating quantum dots have been proposed and may be produced, for example, by including the quantum dots in a suspension polymerisation procedure. One example of such a technique is disclosed in WO 2005/021150 (The University of Manchester) which leads to beads having a size of 0.5 microns upwards.
[0012] Typically one population of quantum dot is added to a single polymerisation reaction. All polymer particles produced in a batch from a polymerisation reaction will contain statistically approximately the same number of quantum dots with the average number of quantum dots per polymer particle being determined by the reagent ratios selected in the polymerisation procedure.
[0013] Since the number of Quantum Dots per particle is relatively similar it is not trivial to distinguish between two different polymer particles produced in the same polymerisation reaction. This is, in some respects, an advantage in that the product of one polymerisation reaction can be made to be detectably different from that of another polymerisation reaction so the two batches can be used as different labelled beads. However this approach means that one polymerisation reaction produces one batch of optically coded polymer particles. By extension, to generate for example ten differently encoded beads would require ten different polymerisation reactions. For utility in optically encoded systems a large number of encoded microbeads are required which in turn would require a large number of polymerisation reactions to be carried out.
[0014] In order to overcome this disadvantage, it is possible (but by no means trivial) to separate the beads obtained in one polymerisation reaction into a number of separate fractions such that the beads in one fraction effectively provide the same signal as each other but beads in different fractions provide signals which can be distinguished from each other by appropriately sensitive equipment. Therefore, in principle, this approach means that a single polymerisation reaction can yield two or more different fractions of labelled beads that can be distinguished from each other.
[0015] It is for example possible to sort the beads (incorporating quantum dots) obtained from one polymerisation reaction on the basis of the intensity of emission of each bead using a rapid sorting procedure such as a Fluorescence Activated Cell Sorter (FACS). Here the FACS instrument would be set to include, for example, emissions between two intensity levels and to exclude emissions above and below these levels - so-called “gating”. One sorting procedure would then, for example, generate three different populations of beads. A quantity between a high and low cut-off level and two subsequent batches one above the higher cut off level and one below the lower cut-off level. However because the intensity cut-off point between one intensity level and the next is a continuum, sorting from one batch to another may result in some particles being placed in a different batch from one run to another i.e. the code fails.
[0016] This problem would be further exacerbated by the use of multiple machines where different machines will not possess exactly the same intensity calibration levels. A possible way round this problem would be to carry out a number of sorts based on intensities and simply discard particles that lie to close to a cut off point. However such an approach would be extremely time consuming (even with the phenomenal speed of FACS) and also result in the wastage of considerable amounts of materials (i.e. of encoded beads).
[0017] It is therefore an object of the present invention to obviate or mitigate the above mentioned disadvantages.
SUMMARY OF THE INVENTION
[0018] According to the present invention there is provided a labelled polymeric bead wherein individual beads comprise:
(a) a primary particle formed of a synthetic polymeric material, and (b) at least one secondary particle entrapped within the primary particle of the bead and being comprised of a synthetic polymer material incorporating reporter moieties, preferably at least around 500 reporter moieties.
[0021] Beads in accordance with the invention are capable of providing a detectable signal (generated by the reporter moieties on application of an appropriate stimulus) which is dependent on the total number of reporter moieties in the bead which in turn is dependent on the combination of:
(a) the number of secondary-particles in the primary particle; and (b) the number of types of secondary-particle in the primary particle.
[0024] As described more fully below, beads in accordance with the invention may easily be produced having different combinations of secondary-particles. Such beads (i.e. those having different combinations of secondary-particles) will contain significantly different total numbers of reporter moieties and are therefore readily distinguishable from each other.
[0025] Preferably the secondary particles include at least one reporter moiety and more preferably a plurality thereof. Generally there will be 1 to 1,000,000 secondary particles in each primary particle although more typically the number of secondary particles (per primary particle) will be 2 to 10,000, e.g. 2 to 5,000. For many embodiments of the invention there will be 5 to 100 secondary particles in each primary particle. Each secondary particle will generally contain at least around 500 reporter moieties to ensure that a detectable signal is provided by each secondary particle. Preferably each secondary particle contains at least around 750, more preferably at least 1000, and most preferably at least 10,000 reporter moieties. More preferably each secondary particle contains at least 100,000 (e.g. at least 1000000) reporter moieties. It can therefore easily be seen that beads containing (in the primary particle) different numbers of secondary will contain significantly different total numbers of reporter moieties so that such beads can be readily distinguished from each other.
[0026] Generally the primary particles will have a maximum cross-sectional dimension of 500 μm, e.g. 2 to 500 μm, e.g. 5 to 200 μm. Typically, the secondary particles will generally have a maximum cross-sectional dimension of 0.2 to 2 μm.
[0027] In a preferred embodiment of the invention, the reporter moieties (in the secondary particles) are quantum dots. The quantum dots may, for example, be core, core-shell or core-multi shell quantum dots. Other types of reporter moieties may for example be used, e.g. luminescent dyes, phosphors such as inorganic lanthanides, fluorescent compounds such as rhodamine, coloured/chromophoric compounds, other “up converting materials”, Raman active compounds such as nitrile-containing compounds, NMR distinguishable isotopic labels such as 14 N/ 15 N nitrogen labelled compounds. With specific reference to fluorescent dyes and quantum dots, it is possible to use one tyre of dye or quantum dot which excites another type of dye or quantum dot by Fluorescence Resonance Energy Transfer (FRET). Reporter moieties can also include metallic particles/clusters (such as silver and gold particles), magnetic particles, radioisotopic labels or other compounds which possess a specific property/functionality that can be readily distinguished by a spectroscopic/analytic/non-destructive technique. An example of such a functional group containing reporter material would be an aldehyde or a nitrile both of which can be readily identified by infrared and Raman spectroscopy respectively. A further example would be a reporter material containing fluorine which can be identified by infrared and Raman spectroscopy.
[0028] The secondary particles (which are ultimately incorporated in the primary particles) may be formed by incorporating the reporter moieties in a polymerisation reaction which yields particles (e.g. having a diameter of 0.2 to 2.0 μm) incorporating the reporter moieties. Examples of polymerisation methods that may be used include suspension, dispersion, emulsion, living, anionic, cationic, RAFT, ATRP, bulk, ring closing metathesis and ring opening metathesis or else by any other method of incorporation into the polymer matrix of the larger polymeric particles. The polymerisation reaction will result in secondary particles containing statistically similar amounts of the reporter moieties.
[0029] The reporter moieties can be irreversibly incorporated in the secondary particles in a number of ways, e.g. chemical, covalent, ionic, physical (e.g. by entrapment) or any other form of interaction.
[0030] The secondary particles thus obtained can then be incorporated in a further polymerisation reaction to form primary particles incorporating a plurality of the secondary particles. Examples of polymerisation methods that may be used include suspension, dispersion, emulsion, living, anionic, cationic, RAFT, ATRP, bulk, ring closing metathesis and ring opening metathesis or else by any other method of incorporation into the polymer matrix of the larger polymeric particles.
[0031] The primary matrix of the secondary particles and/or the polymer matrix of the primary particles can be inert. Alternatively either or both matrices may be produced with a functionalised monomer. Alternatively either or both matrices may be functionalised after polymerisation.
[0032] The primary and secondary polymeric particles produced by these procedures may have any shape/morphology or 3-dimensional structure. Thus, for example, the particles may be spherical, disc-like, rod-like, ovoid, cubic or rectangular (many other configurations are also possible).
[0033] The polymerisation reaction for forming the primary particles may be effected using secondary particles of the same “type” (i.e. containing substantially the same numbers of the same reporter moieties), e.g. as obtained from a single polymerisation reaction for producing the secondary particles. For the purposes of the present invention, the term “same type” as applied to a sub-particle refers to sub-particles that contain approximately the same population of reporter moieties, i.e. within a narrowly defined distribution. Alternatively the polymerisation procedure for forming the primary particles may be effected using a mixture of different types of secondary particles, e.g. differing in numbers and/or nature of the reporter moieties.
[0034] The result of incorporating the secondary particles into the primary particles is that the resulting beads possess unique combinations of ‘quanta’ of one or more reporter material resulting in a distinct encoding pattern for that particular bead.
[0035] For example it is possible to mix separate batches of secondary particles containing (only) red quantum dots with batches containing further (separate) batches of secondary particles containing blue quantum dots and green quantum dots to give a population of secondary particles in the ratio of 10 blue:5 red:1 green.
[0036] These will then be incorporated into primary particles by any suitable polymerisation reaction to generate beads (containing the secondary particles) which possess distinct readable codes/signatures for example based on the colour and intensity of the three colours/channels of QD emissions (i.e. the number/‘quanta’ of smaller beads of each colour within each bigger bead). Beads resulting from this procedure having differing contents of secondary particles (e.g. different numbers of any one type of secondary particle) are readily distinguished from each other because of the significantly different total number of reporter moieties present in the bead. As such, the beads from the polymerisation reaction can readily be sorted into different fractions with the beads of each fraction being essentially identical to each other in turns of their detection characteristic but readily detectably different from beads in other fractions.
[0037] Differently sized reporter material-containing secondary particles can also be used to encode the larger polymeric particles. For example some blue QD-containing secondary particles of 2 μm and some red QD-containing smaller beads of 10 μm may be incorporated into the same population of primary particles. The resulting beads may then be distinguished from one another on the basis of both the size and colour of the secondary particles they contain.
[0038] Differently shaped reporter material-containing secondary particles can also be used to encode the primary particles. For example some blue QD-containing spherical secondary particles and some red QD-containing cubic secondary particles may be incorporated into the same population of primary particles. The resulting beads may then be distinguished from one another on the basis of both the shape and colour of the secondary particles they contain.
[0039] In addition the incorporation of specifically shaped reporter material-containing secondary particles into primary particles may confer specific shape related properties e.g. a dipole moment or a diffraction property, upon the resulting bead.
[0040] The primary and/or secondary particles may be chemically inert or alternatively may be chemically reactive/functionalised. The chemical functionality may be introduced during the construction of the particle, for example by the incorporation of a chemically functionalised monomer, or alternatively chemical functionality may be introduced in a post particle construction treatment for example a chloromethylation reaction. Additionally chemical functionality may be introduced by a post particle construction polymeric graft or other similar process whereby chemically reactive polymer(s) are attached to the outer layers of the reporter material containing polymeric particles. It will be obvious to those skilled in the art that more than one such post construction derivatisation process may be carried out to introduce chemical functionality onto/into the reporter material containing polymeric particles.
[0041] Although the invention has been described with specific reference to beads comprising primary particles and secondary particles, it should be understood that other constructions are within the ambit of the invention. Thus, for example, beads in accordance with the invention may comprise primary, secondary and tertiary particles. More specifically, the tertiary particles may contain reporter moieties, the secondary particles may contain various combinations of the tertiary particles, and the primary particles contain various combinations of the secondary particles.
[0042] A further possibility is a bead comprising a primary particle incorporating one or more secondary particles (each, in turn, incorporating one or more reporter moieties) and at least one polymeric shell provided around the primary particle. Each polymeric shell may itself incorporate one or more secondary particles. Thus, for example, assume that the primary particle is spherical. In this case, there may be one or more concentric polymer outer shells provided around the primary particle, each such shell incorporating one or more secondary particles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] The invention will be further described by way of example only with reference to the accompanying drawings in which:
[0044] FIG. 1 schematically illustrates the structure of labelled beads in accordance with the invention and spectra obtained using examples of such particles;
[0045] FIG. 2 schematically illustrates intensity outputs of (a) labelled beads in accordance with the invention, and (b) labelled beads of the prior art;
[0046] FIG. 3 schematically illustrates intensity-based sorts of (a) labelled beads in accordance with the invention, and (b) labelled beads of the prior art;
[0047] FIG. 4 is a scanning electron microscopy (SEM) image of QD-containing dispersion beads produced using the large-scale dispersion polymerisation procedure set out below;
[0048] FIG. 5 ( a ) a confocal microscope image of a suspension bead encapsulated within a thin film of PDMS;
[0049] FIG. 5 ( b ) a cross-sectional fluorescence emission fingerprint of the bead of FIG. 5 ( a ) (fingerprint taken along the line shown in FIG. 5 ( a ));
[0050] FIG. 6 is a vertical view down a PDMS-based rod that encapsulates QD-containing beads generated using a small scale suspension polymerisation reaction as set out below;
[0051] FIG. 7 shows superimposed PL spectra of a sample of QD-containing dispersion beads and a sample of suspension beads that contain the QD-containing dispersion beads; and
[0052] FIG. 8 is a confocal microscopy image of a bead from within a sample of suspension beads that contain the QD-containing dispersion beads (made according to entry 7 of Table 2 below).
DETAILED DESCRIPTION OF THE INVENTION
[0053] Reference is made firstly to FIG. 1 (A) which, at the right hand side thereof, illustrates one embodiment of a labelled bead (“Suspension Polymerisation Particle”) in accordance with the invention. This particle, which may for example have a size of 5-200 μm, is comprised of a polymeric matrix in which are embedded a plurality of secondary particles (“Dispersion Polymerisation Beads”) each incorporating a population of quantum dots.
[0054] Each of these secondary particles may incorporate quantum dots of a single type but the type may vary between secondary particles. Thus for example some secondary particles (the “red secondaries”) may incorporate a population of quantum dots that emit red light when excited by UV radiation, some (the “blue secondaries”) may incorporate quantum dots that emit blue light and others (the “green secondaries”) may incorporate quantum dots that emit green light.
[0055] Secondary particles that contain the same type of quantum dot will generally all contain approximately the same number thereof. However this number may be different for quantum dots of a different type. Thus, for example, the aforementioned “red secondaries” will each contain approximately the same number of quantum dots. However the “green secondaries” may contain a significantly different number of quantum dots (although the “green secondaries” will contain approximately the same number of quantum dots as each other). Similarly for the “blue secondaries”.
[0056] It will be appreciated that, to produce the illustrated labelled particle, individual collections of red, green and blue sub-particles (“secondaries”) are produced by dispersion polymerisation techniques using a reagent system incorporating quantum dots of the appropriate “colour”.
[0057] Fractions of red, green and blue “secondaries” are then incorporated into a suspension polymerisation procedure to produce a collection of labelled particles of the type illustrated in FIG. 1A . This collection may then be readily sorted into fractions with the members of any one fraction containing exactly the same number of the different types of sub-particle.
[0058] FIG. 1 (B) illustrates how labelled beads in accordance with the invention may readily be distinguished from each other in the case where individual beads have differing contents of secondary particles.
[0059] For the purposes of the following description, the beads depicted as (i)-(iii) in FIG. 1 (B) are assumed to contain the following ratios of secondary particles of the indicated type (although in practice larger numbers of the various types of secondary particles are likely to be present).
Red Secondary Blue Secondary Green Secondary Bead No. Particles Particles Particles (i) 1 2 2 (ii) 2 2 3 (iii) 3 1 2
[0060] Again for the purposes of illustration, FIG. 1 (B) shows the particles (i)-(iii) being illuminated with UV light which on emission from the particle is analysed by a detector to provide the emission spectra illustrated at the right hand side of FIG. 1 (B), for which blue emission is represented by the left hand peak, green emission by the middle peak and red emission by the right hand peak.
[0061] It will be appreciated from FIG. 1 (B) that particle (i) has a particular emission spectrum as governed by the number of red, blue and green secondary particles present in the bead. The spectrum of particle (i) is different from that of particles (ii) and (iii) which in turn are different from each other.
[0062] Thus the individual particles (i)-(iii) are readily distinguishable from each other.
[0063] FIG. 2 schematically illustrates how a collection of beads in accordance with the invention in which some of the beads contain a different number of secondary particles (incorporating quantum dots as reporter moieties) than others are much more readily distinguished from each other than are labelled beads of the prior art which comprise a single particle incorporating differing numbers of reporter moieties.
[0064] More specifically, the upper graph of FIG. 2 relates to the prior art labelled beads and the lower graph relates to labelled beads of the invention. The prior art labelled beads have been produced by a suspension polymerisation reaction conducted with quantum dots which has resulted in a collection of labelled beads containing a range of individual quantum dots. The “x-axis” of the upper graph in FIG. 2 represents (going from left to right) increasing numbers of quantum dots in the individual polymer particles of the prior art beads. The “y-axis” represents intensity of emission (arbitrary units). It will be seen from the upper graph of FIG. 2 that (for the prior art particles) a plot of number of quantum dots in the (prior art) beads vs intensity is a smooth curve.
[0065] Consider now, in contrast, the lower graph of FIG. 2 which relates to labelled beads of the invention. The “x-axis” of this graph represents the number of secondary particles in the beads and the “y-axis” again represents intensity (in arbitrary units). It can be seen that, for the labelled beads of the invention, a plot of number of secondary particles vs intensity is stepped such that each additional secondary particle produces a distinct rise in the intensity of the beads.
[0066] Reference is now made to FIG. 3 which compares intensity based sorts of the prior art labelled beads and those of the invention. Graphs (A) and (B) of FIG. 3 are effectively the same plots as represented by the upper graph of FIG. 2 . Graph (C) of FIG. 3 is effectively the same plot as represented by the lower graph of FIG. 2 .
[0067] Assume that it is desired to sort the prior art beads into different fractions. Graph (A) represents an intensity based sort carried out at two different intensities. In principle, this gives three populations of beads a, b and c. However beads having intensities close to the “sorting intensities” may be mis-sorted if the procedure is carried out again, for example after subjecting the beads to a biological assay procedure, and the difference in emission intensity between individual beads is very small.
[0068] For the purposes of Graph (B) it is assumed that the prior art particles have initially been sorted at Intensities I 1 and I 2 into three fractions a, b and c (as represented by Graph (A). Each fraction is now subjected to a secondary sort. More specifically, fraction a is subjected to a sort at intensity I 3 (<I 1 ). This sort separates fraction a into two sub-fractions a 1 and a 2 . The latter fraction is then discarded.
[0069] Fraction c is subjected to a secondary sort at an intensity I 4 (>I 2 ) so that two sub-fractions c 1 and c 2 are generated (having intensities below and above I 4 respectively). Fraction c 1 is discarded.
[0070] Consider now the situation represented by Graph C for particles in accordance with the invention. Four primary sorts at different intensities give five distinctly different bead populations readily discriminated from one another on the basis of their quantum dot emission intensities. This procedure is highly efficient both in terms of the number of sorting procedures required and in the fact that no material need be discarded.
[0071] The invention is illustrated by the following non-limiting Examples.
EXAMPLES
1. Materials
[0072] Cadmium oxide, oleic acid, octadecene, divinylbenzene, styrene, sulfur, poly (N-vinylpyrrolidone) (PVP, molecular mass: 40,000), poly (vinyl alcohol) (PVA, molecular mass: 85,000), and 1,1′-azobis-(cyclohexanecarbonitrile) (ACHN) were purchased from Aldrich, Fisher and Lancaster and were used without any further purification. Methanol, toluene, acetone and chloroform were purchased from VWR and used as received. Deuterated chloroform was purchased from Goss Scientific and used as received.
[0073] All syntheses and manipulations were carried out under a dry oxygen-free argon or nitrogen atmosphere using standard Schlenk and glove box techniques. All solvents were analytical grade and distilled from appropriate drying agents prior to use (Na/K-benzophenone for THF, Et 2 O, toluene, hexanes, pentane; magnesium for methanol and ethanol and calcium hydride for acetone).
2. Synthesis of CdSe/ZnS and CdSe Nanoparticles
[0074] CdSe nanoparticles were synthesized the method disclosed in WO-A-05106082.
[0000] Preparation of CdSe-HDA Capped Nanoparticles
[0075] Hexadecylamine HDA (500 g) was placed in a three-neck round bottomed flask and dried and degassed by heating to 120° C. under a dynamic vacuum for >1 hour. The solution was then cooled to 60° C. To this was added 0.718 g of [HNEt 3 ] 4 [Cd 10 Se 4 (SPh) 16 ] (0.20 mmols). In total 42 mmols, 22.0 ml of TOPSe and 42 mmols, (19.5 ml, 2.15 M) of Me 2 Cd·TOP was used. Initially 4 mmol of TOPSe and 4 mmols of Me 2 Cd·TOP were added to the reaction at room temperature and the temperature increased to 110° C. and allowed to stir for 2 hours. The reaction was a deep yellow colour, the temperature was progressively increased at a rate of ˜1° C./5 min with equimolar amounts of TOPSe and Me 2 Cd·TOP being added dropwise. The reaction was stopped when the PL emission maximum had reached ˜600 nm, by cooling to 60° C. followed by addition of 300 ml of dry ethanol or acetone. This produced a precipitation of deep red particles, which were further isolated by filtration. The resulting CdSe particles were recrystallized by re-dissolving in toluene followed by filtering through Celite followed by re-precipitation from warm ethanol to remove any excess HDA, selenium or cadmium present. This produced 10.10 g of HDA capped CdSe nanoparticles. Elemental analysis C=20.88, H=3.58, N=1.29, Cd=46.43%. Max PL=585 nm, FWHM=35 nm. 38.98 mmols, 93% of Me 2 Cd consumed in forming the quantum dots.
3. Preparation of CdSe/ZnS-HDA Capped Nanoparticles
[0076] HDA (800 g) was placed in a three neck round-bottom flask, dried and degassed by heating to 120° C. under a dynamic vacuum for >1 hour. The solution was then cooled to 60° C., to this was added 9.23 g of CdSe nanoparticles that have a PL maximum emission of 585 nm. The HDA was then heated to 220° C. To this was added by alternate dropwise addition a total of 20 ml of 0.5M Me 2 Zn·TOP and 0.5M, 20 ml of sulfur dissolved in octylamine. Three alternate additions of 3.5, 5.5 and 11.0 ml of each were made, whereby initially 3.5 ml of sulphur was added dropwise until the intensity of the PL maximum was near zero. Then 3.5 ml of Me 2 Zn·TOP was added dropwise until the intensity of the PL maximum had reached a maximum. This cycle was repeated with the PL maximum reaching a higher intensity with each cycle. On the last cycle, additional precursor was added once the PL maximum intensity been reached until it was between 5-10% below the maximum intensity, and the reaction was allowed to anneal at 150° C. for 1 hour. The reaction mixture was then allowed to cool to 60 ° C. whereupon 300 ml of dry “warm” ethanol was added which resulted in the precipitation of particles. The resulting CdSe—ZnS particles were dried before re-dissolving in toluene and filtering through Celite followed by re-precipitation from warm ethanol to remove any excess HDA. This produced 12.08 g of HDA capped CdSe—ZnS core-shell nanoparticles. Elemental analysis C=20.27, H=3.37, N=1.25, Cd=40.11, Zn=4.43%; Max PL 590 nm, FWHM 36 nm.
4. Ligand Exchange
[0077] Quantum dots were dissolved in 1,4-dioxane, 4 ml, containing a large excess of the polymerisable ligand, 1 mmol. The solution was then stirred for 20 hours at room temperature. Centrifugation and drying resulted in ligand exchanged quantum dots (14 mg for the p-vinylbenzylDOPO and 10 mg for p-octenylDOPO batches). Product structures were confirmed by 1 H and 13 C NMR and APCI mass spectrometry.
5. Small-scale Suspension Polymerisation Procedure 1
[0078] Aqueous polvinylalcohol (PVA) solution (20 ml, 1% wt/wt, 87-89% hydrolyzed PVA, average MW 85,000-146,000) was prepared and transferred to the reaction vessel (screw cap boiling tube attached to a N 2 /vacuum manifold system) and degassed with N 2 for 20 minutes. A monomer mixture—styrene (10 mmol), divinylbenzene and quantum dots—was prepared and stirred for 5 minutes. AIBN (76 μmol) was added to the monomer mixture then the resultant mixture was stirred for a further 15 minutes with N 2 degassing. The dark orange monomer solution (colour due to the quantum dots) was added to the PVA solution while rapidly stirring with a cross-shaped magnetic stirrer. A two phase system resulted with orange droplets being suspended in the colourless aqueous PVA solution. The suspension was stirred at room temperature for 30 minutes before the temperature was increased to 70° C. and stirring was continued for a further 4 hours. The resin beads were then collected over a 38 μm sieve and washed in situ with copious amounts of water. The damp beads were then transferred to a sintered funnel and washed with methanol (100 cm 3 ), MeOH/THF, 1/1 (100 cm 3 ), THF (100 cm 3 ), CH 2 Cl 2 (100 cm 3 ) and acetone (100 cm 3 ).
6. Small-Scale Dispersion Polymerisation Procedure 2
[0079] A reaction medium comprising poly(N-vinylpyrrolidone), average MW 55000, (0.2 g) dissolved in a 95:5 ethanol:water mixture (10 ml) was placed in a reaction tube of a 12-place stirring carousel. To this reaction medium was added a monomer mixture comprised of 10 mmol of monomer/crosslinker in total. By way of example (entry 5 below) the monomer comprised of styrene (2 mmol), divinylbenzene (8 mmol) AIBN (0.01 g) and quantum dots (5 mg). Nitrogen was then bubbled though the resultant mixture for 20 minutes and the solution kept under a nitrogen atmosphere until the reaction had proceeded to completion. The solution was gently stirred (approximately 150 rpm) and brought to and maintained at a temperature of 60° C. for 16 hours. The beads were then collected and washed by centrifugation
TABLE 1 Reaction PL λmax; Entry Monomers Quantum Dot Scale intensity 1 S/DVB 5 mg CdSe/ZnS; 590 nm 10 ml 570; 2200 100/0 2 S/DVB 5 mg CdSe/ZnS; 590 nm 10 ml 564; 3400 (98/2) 3 S/DVB 5 mg QDQW 10 ml 506; 2570 (98/2) ZnS/CdSe/ZnS; 494 nm 4 S/DVB 5 mg QDQW 10 ml 506; 3334 (0:100) ZnS/CdSe/ZnS; 494 nm 5 S/DVB 5 mg QDQW 10 ml 506; 3906 (20:80) ZnS/CdSe/ZnS; 494 nm 6 S/DVB 5 mg QDQW 10 ml 504; 2147 (40:60) ZnS/CdSe/ZnS; 494 nm
Representative examples of quantum dot-containing beads made according to the above “Small-scale dispersion polymerisation procedure 2” and associated PL data. (S—styrene; DVB—divinylbenzene and DOPO—dioctylphosphine oxide)
[0080] 7. Large-Scale Dispersion Polymerisation Procedure
[0081] Styrene (481 mmoles, 55 cm 3 ), divinylbenzene (9.0 mmoles, 1.37 ml), AIBN (3.0 mmoles, 0.5 g) and CdSe/ZnS (hexadecylamine ligand) quantum dots (100 mg) were mixed together. This mixture was then added to a reaction medium comprising poly(N-vinylpyrrolidone), average MW 55000, (10 g) dissolved in a 95:5 ethanol:water mixture (500 ml). Nitrogen was then bubbled though the resultant mixture for 20 minutes and the solution kept under a nitrogen atmosphere until the reaction had proceeded to completion. The solution was gently stirred (approximately 150 rpm) and brought to and maintained at a temperature of 60° C. for 24 hours. The beads were then collected and washed by centrifugation.
8. Procedure for Encapsulating QDs and QD-Containing Beads in Polydimethylsiloxane (PDMS)-Based Films and Rods
[0082] PDMS (Sylgard 184, Dow Corning) was mixed and prepared as per the manufacturer's instructions, i.e. 10 parts base were mixed with 1 part curing agent and this mixture was then placed under high vacuum until any bubbles had been removed. A small amount of QDs or QD-containing beads (produced by a dispersion or suspension polymerisation reaction) was then added to the PDMS mixture (˜1 mg in 1 ml). The resultant mixture was stirred thoroughly and again placed under high vacuum to remove any bubbles.
[0083] Thin films were prepared on a microscope slide, by either spreading the PDMS preparation with a spatula or else by placing a drop of the PDMS preparation onto a slide and pressing a cover slip on top. Thin films prepared by either of these two methods were then heated in an oven at 100° C. for 1 hour. Thicker films could similarly be prepared by pouring the liquid PDMS preparation into a suitable mould, e.g. a petri dish, and heating the PDMS preparation in situ at 100° C. Rods were prepared by pouring the PDMS preparation into a glass vial (1 cm diameter×5 cm high) and heating the PDMS preparation in situ at 100° C. for 1 hour.
9. Synthesis of Quantum Dot Doped Polystyrene Beads
[0084] CdS doped polystyrene latexes were synthesized via a modification of the suspension polymerization method. PVP (0.25 g) as the stabilizer was first dissolved in 40 ml PVA aqueous solution (wt 10%). The mixture was heated to 50° C. under N 2 and a solution of CdS nanoparticles (25 mg), divinylbenzene (20 mg) and ACHN (25 mg) in styrene monomer (2.5 g) was injected into the reaction mixture with vigorous stirring. The reaction was kept at 70° C. for 6 hours. After cooling to room temperature, the solution was purified by centrifugation and redispersion with toluene and water using the method previously described. The size of polymer latexes is strongly dependent on the stirring speed and PVP concentration. With this method, particles with a size range from 100 nm to 500 μm could be obtained.
10. Preparation of the Beads Containing the Quantum Dot-Containing Beads
[0085] A small scale suspension polymerisation reaction procedure was carried out exactly as described above with styrene (8 mmol) and divinyl benzene (2 mmol) as the monomer phase (10 mmol in total) and AIBN (76 μmol). The only difference in the procedure employed was that an aliquot of QD-containing dispersion beads (6.5 mg) were added to the monomer mixture, in place of QDs, just prior to the addition of the AIBN.
[0086] In addition it was possible to use this method with other ratios of styrene and divinylbenzene and also other monomers in place of styrene and divinylbenzene as the following Table indicates. In all instances the total number of moles in the monomer phase was 10 mmol.
TABLE 2 PL of the beads containing the Dispersion Beads quantum dot- Suspension (made according to containing beads Entry Monomers Table 1 entry 3) λmax; intensity 1 S/DVB 5 mg (494 nm); S/DVB, beads 496; 2592 99/1 99:1 2 S/DVB 5 mg (494 nm); S/DVB, beads 496; 3267 98/2 99:1 3 S/DVB 5 mg (494 nm); S/DVB, beads 487; 892 80/20 99:1 4 S/DVB 5 mg (494 nm); S/DVB, beads 487; 1113 60/40 99:1 5 S/DVB 5 mg (494 nm); S/DVB, beads 487; 3313 0/100 99:1 6 MMA/EGDM 5 mg (494 nm); S/DVB, beads 496; 1391 99/1 99:1 7 MMA/EGDM 5 mg (494 nm); S/DVB, beads 498; 3334 98/2 99:1 8 MMA/EGDM 5 mg (494 nm); S/DVB, beads 498; 2030 80/20 99:1 9 MMA/EGDM 5 mg (494 nm); S/DVB, beads 499; 1130 60/40 99:1 10 MMA/EGDM 5 mg (494 nm); S/DVB, beads 498; 1739 0/100 99:1
Representative examples of beads that contain quantum dot-containing beads made according to the “Preparation of beads containing the quantum dot-containing beads” procedure and associated PL data. (S—styrene; DVB—divinylbenzene; MMA—methyl methacrylate; EGDM—ethylene glycol dimethacrylate).
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A labelled polymeric bead wherein individual beads comprise a primary particle formed of a synthetic polymeric material, and at least one secondary particle entrapped within the primary particle of the bead and being comprised of a synthetic polymer material incorporating reporter moieties.
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FIELD OF THE INVENTION
This invention relates to pile driving generally and, in particular, to a method of and apparatus for measuring the driving resistance of a pile and the velocity imparted to the pile by a blow from a pile driving hammer.
BACKGROUND OF THE INVENTION
Accelerometers are used to measure the acceleration of piles being driven into the earth by a pile driving hammer. This information is useful in measuring the efficiency of the pile driving hammer, as well as driving resistance of the pile, along with other useful measurements. Primarily, driving resistance is significant in that it must reach a predetermined level in order for the pile to adequately bear the desired load.
Conventional systems for measuring driving resistance and pile velocity utilize self-generating-type accelerometers, which, as the name implies, self-generate direct current electric signals. A quartz or piezoelectric crystal is compressed by the mass of the accelerometer during movement of the pile, producing electrical impulses proportional to the acceleration of the pile. The acceleration signals produced by the accelerometer are recorded and subsequently electronically integrated on separate equipment to produce a velocity measurement. The velocity measurements are in turn, electronically integrated a second time to produce a measurement of pile displacement. The number of recorded blows are determined for each linear unit of displacement to arrive at a "blow count". The "blow count" determines an average displacement per hammer blow for the pile. The force applied to the pile by the hammer is sensed simultaneously by separate apparatus. The force and average displacement can be related to driving resistance by known formulas which recognize soil conditions, pile configuration and desired depth of penetration. This final calculation is currently performed manually, usually on a "bearing graph".
However, conventional systems suffer from general inherent limitations. Specifically, self-generating accelerometers sometimes display a "zero offset error" in the acceleration signal during or just after the hammer blow to the pile. FIG. 1A graphically represents, in Line A, the force applied to a pile during a hammer blow. FIG. 1B graphically illustrates, in Line B, an accurate representation of the velocity of the pile as a result of the hammer blow. Line C in FIG. 1B shows a ramped portion constituting the integral of the "zero offset error". This ramp error distorts the observed displacement of the pile when the velocity signal is integrated, prevents an accurate measurement of driving resistance, as well as increasing or decreasing the apparent number of hammer blows depending on the direction of the ramp.
As a result, it has been customary to visually observe displacement of the pile and to manually record blows per unit of displacement to arrive at a "blow count". This method is inherently subject to human error and reduces the reliability of the computation of driving resistance, and is therefore unsatisfactory. Further, it is not possible using this method to calculate the driving resistance for a selected hammer blow, only an average figure over a certain amount of displacement.
Self-generating accelerometers, because they operate by generating direct current electric power, also inherently generate a displacement error in the acceleration reading caused by rapid movement through the ambient magnetic field.
Therefore, it is an object of this invention to provide improved method and apparatus for measuring the driving resistance and velocity of piles during driving.
It is another object of this invention to provide such an improved accelerometer that does not exhibit a zero offset error and displacement error when measuring the acceleration of piles being driven, thereby allowing accurate measurements of the blow count, velocity and displacement imparted to the pile by the hammer blow.
It is yet another object of this invention to provide an improved method and apparatus for measuring the driving resistance and velocity of a pile for selected individual hammer blows during driving.
Therefore, these and other objects and advantages of this invention will be apparent to those skilled in the art from a consideration of this specification, including the attached drawings and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a graphical representation of the force applied to a pile by a pile driving hammer.
FIG. 1B is a graphical representation of the first integral of the acceleration signal from an accelerometer attached to a pile acted on by the force of FIG. 1A, showing the zero offset error produced by a self-generating accelerometer compared to the actual velocity of the pile.
FIG. 2A is a top view of the apparatus of this invention used to measure the acceleration imparted to the pile by the pile driving hammer.
FIG. 2B is a side view of the apparatus of FIG. 2A.
FIG. 3 is a schematic block diagram of the apparatus used to practice the method of this invention.
DETAILED DESCRIPTION OF THE INVENTION
The apparatus of the present invention constitutes a strain gage-type accelerometer as opposed to the self-generating-type previously employed. Strain gage-type accelerometers utilize one or more strain gages attached to an accelerometer body, which is in turn mounted on the object to be measured. Movement of the pile induces deformation and stress in the accelerometer body, which is detectable by the strain gages and is proportional to acceleration. Alternating current electricity is used to excite the strain gages.
Existing strain gage accelerometers have been used in laboratories and on small scale models to measure acceleration under controlled conditions. Heretofore, strain gage accelerometers have been considered unusable under the harsh conditions experienced in pile driving operations. One limitation has been that existing designs have a bandwidth which is too narrow for the accuracy required in pile driving. The bandwidth of a strain gage accelerometer is measured from 0 Hz (i.e., direct current) up to through the frequency of the alternating current electricity used to excite the accelerometer. However, this frequency must not be more than 1/3 to 1/2 of the inherent resonant frequency of the accelerometer body. Otherwise the vibration of the body interfers with the operation of the accelerometer. Because of the small size of existing accelerometers, this natural resonant frequency has been unnecessarily low and therefore the bandwidth of the accelerometer has been limited to approximately 5,000 Hz.
In addition, conventional strain gage accelerometers have been shown to be too fragile for pile driving applications in that the strain gages and the electrical leads frequently are dislodged from the accelerometer body during driving. However, what has not been appreciated prior to the present invention is that strain gages accelerometers do not produce the zero offset error and displacement error inherent in the self-generating accelerometers.
Therefore, according to the present invention, a strain gage accelerometer, generally indicated by the member 12, is utilized which has a natural resonant frequency for the accelerometer body that has been significantly increased over conventional designs. Specifically, a natural resonant frequency range of 30,000 Hz is utilized which enables the bandwidth of the accelerometer to be increased to 10,000 Hz, significantly improving the accuracy of the data collected. At the same time the increase in size of the accelerometer body needed to raise the resonant frequency produces a more rugged and durable configuration able to withstand driving conditions.
Various types of strain gages accelerometers are known and may be applied to the method and apparatus of this invention. The illustrated embodiment utilizes an accelerometer body 14 attached by bolt 16 to the pile 10, which pile is constructed of concrete or like material, as shown in FIGS. 2A and 2B. Of course, this invention is equally applicable to a pile constructed of metal, such as steel, in which case block 14 may be welded or otherwise suitably affixed to the pile. Cantilever beam 18 extends transverse to the longitudinal axis of the pile and is integrally formed as part of body 14 of the accelerometer.
The material of the block possesses high internal dampening characteristics which quickly attenuate the vibration of the cantilever beam induced by the sudden acceleration of the pile. Preferably, the block is constructed of an alloy of manganese and copper which has dampening characteristics similar to a material such as lead, but has the strength to withstand the rigorous conditions experienced while mounted on the pile. Previous strain gage accelerometers did not appreciate the advantages of using this or a similar material.
Four strain gages 20 are attached to the cantilever beam, two mounted on the upper surface and two on the lower surface, preferably at the radius at which the beam joins the main body of block 14. More or fewer strain gages may be used as are found useful in a particular configuration or design. Also the strain gages may be connected in a different arrangement or attached on other portions of the accelerometer body. Electrical leads 21 connect the strain gages in a Wheatstone bridge configuration. The leads are securely fastened to the body and extend remotely to other apparatus now shown in FIG. 1, constituting the remainder of the invention for processing and transmitting the signals produced by the accelerometer. Separate force measuring devices (not shown) of conventional design, are also mounted on the pile to record the impact of selected hammer blows in conjunction with the remainder of the apparatus hereinafter discussed.
In FIG. 3, strain gages 20 are shown schematically connected to oscillator 22 which, as previously discussed, generates alternating current electrical signals to excite the strain gages of the accelerometer, preferably at 10,000 Hz. Stresses in cantilever beam 18 induced by longitudinal movement of the pile will cause the amplitude of the output of the strain gages to fluctuate in a manner which can be used as a measure of acceleration.
The output of the strain gages 20 is connected to amplifier 24 to provide a high strength output signal. The amplified signals from the amplifier are transmitted to phase sensitive demodulator 26 which converts the output of strain gages 20 to signals in which voltage is proportional to acceleration. The output of the demodulator is in turn transmitted to linear integrator 28 which electronically integrates the signals to produce signals in which voltage is directly proportional to velocity, the desired measurement. These signals are in turn transmitted to an analog-to-digital converter 30 which converts the signals into a digital format.
Level detector and time gate 32 monitors the output of integrator 28 such that the analog-to-digital converter will be activated only when voltage levels are detected above a predetermined threshold level. In other words, random signals in the absence of movement of the pile under impact of the driver will be ignored by the analog-to-digital converter. In addition, level detector and time gate 32 continues to actuate the analog-to-digital converter for a predetermined time, preferably 80 milliseconds or 160 milliseconds. This insures that an adequate amount of the velocity measurement will be taken.
Alternatively, the level detector and time gate may be connected by means of switch 29 to separate apparatus 31 which is a sensor resonsive to the force applied by the hammer, or alternatively, the bending moment of the pile.
Write clock 34 is free-running and connected to analog-to-digital converter 30 and digital memory 32, which stores the digital signals from the converter. As the signals are converted to digital format, the write clock generates a signal, preferably at 12,800 Hz to regulate the rate at which the signals are stored in the memory.
Switch 40 connects the write clock and the memory during driving operations. After a sufficient amount of data has been stored in the memory 33, switch 40 is turned to connect read clock 36 to the memory, for controlling the rate at which the contents of digital memory 33 are transmitted. Preferably, the read clock operates at a rate 1/40th that of the write clock, (i.e. at 320 Hz), so that data signals are transmitted to digital-to-analog converter 42 at a significantly slower rate than the rate at which they are stored. This enables recorders 44 and 46 to be simultaneously connected to the digital-to-analog converter to record the analog velocity signals and to the required bandwidth of the recorders to be reduced by a similar factor. Time clock 38 is connected to read clock 36 and generates signals which are stored on recorders 44 and 46 in conjunction with the analog velocity signals, to provide a real time reference when interpreting the data.
Recorder 44 may constitute a strip chart recorder which enables the pile driver operator to monitor the movement and condition of the pile as the driving is performed. In addition, the pile driver operator is able to identify and eliminate anomolous data from the record which may result from such things as the accelerometer body being loosened on the pile. Errors in the acceleration signal become immediately apparent to the operator, whereas conventional designs delayed access to this information for a substantial period of time. Under the present invention, malfunctions of the apparatus can be corrected immediately. Additionally, the strip chart record can be used to screen many hammer blows and to select one or several for further analysis. Recorder 46 may constitute a magnetic tape recorder which permits the operator to add voice annotation to the record concerning observed hammer performance, steam leaks, pile displacement or blow count information.
The output of recorder 46 is connected to data processsor 47, which may be located adjacent the pile driving site. One advantage of the present invention is that the recorder 46 and data processor 47 may be operated independently of the remainder of the apparatus and if necessary, simultaneously and while disconnected therefrom. Alternatively, and as shown in dotted line in FIG. 3, the output of digital-to-analog converter 42 may be connected directly to the data processor, which includes its own data storage capability. Data processor 47 electronically integrates the velocity signal to provide a measurement of pile displacement for each hammer blow. Since the zero offset error has been eliminated from the data, the data processor is able to determine the exact number of hammer blows electronically by measuring the peaks of velocity or displacement. Data processor 47 is also connected to the force measuring apparatus previously discussed, which transmits to the data processor the force measurements for the hammer blows selected by the operator. The data processor, uses the relationships previously discussed to automatically and electronically calculate driving resistance of the pile, rather than manually as before. Since anomolous data such as the zero offset error has been eliminated, the data processor may be used to calculate the driving resistance based on an average of selected displacement measurements to increase the accurancy. Alternatively, the data processor is capable of calculating the driving resistance for individual selected hammer blows rather than an average. This capability is particularly important as the driving resistance approaches the desired threshold level.
A means is also provided with the system of the present invention to calibrate the accelerometer to compensate for fluctuating operating conditions such as temperature, humidity, etc. or for long term drift of the component values. Specifically, when the block and accelerometer of the present invention are attached under controlled conditions to a calibration object (not shown) and dropped from a known height, a known velocity will be achieved which can be measured upon impact by the method and apparatus hereinabove discussed. Timer 52 in FIG. 3 controls a switch 50 for generating a calibration signal while precision calibration resistor 48 shunts one of the strain gages of the accelerometer. The accelerometer when excited by the oscillator and connected to the shunt resistor for a known period of time, for instance for 5 milliseconds, will generate a simulated acceleration output signal. This simulated acceleration signal is passed through the linear integrator, and compared to the signal generated during the drop from the known height. The ratio of these quantities can be used to generate a calibration factor.
The calibration resistor is again connected by the timer through switch 50 to one of the strain gages under actual operating conditions for a similar period of time. The variation in the simulated acceleration signal from that generated under controlled conditions can be used to compensate for fluctuations in such factors as temperature and humidity which effect the values of the electronic components of the apparatus. Preferably, the calibration consists of adjusting the gain of amplifier 24. Thus, by measuring acceleration, velocity, and displacement in one process, only one calibration of the apparatus is required. Prior systems required a separate calibration for the accelerometer and a second calibration for the remainder of the apparatus required to generate the driving resistance.
The foregoing disclosure and description of the invention is illustrative and explanatory thereof, and various changes in the method steps as well as the details of the illustrated apparatus may be made within the scope of the pending claims without departing from the spirit of the invention.
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A method and apparatus for measuring the driving resistance and velocity of piles during driving utilizing a strain gage accelerometer mounted on the pile. The accelerometer is constructed of a material having high internal dampening characteristics and is excited by alternating current electric signals. The acceleration signals of the accelerometer are electronically integrated to provide a measurement of velocity and an accurate blow count, which may be simultaneously recorded on two separate recording media. The velocity measurements are integrated a second time to derive a measure of pile displacement for selected hammer blows, which in turn enables the driving resistance to be determined. Observation of the velocity measurement during pile driving operations permits anomalous data to be eliminated prior to the calculation of driving resistance.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to construction aids, and, more particularly, to an apparatus for facilitating the installation of suspended ceilings.
2. Description of the Prior Art
The use of suspended ceilings has increased significantly in the construction industry in recent years. Ceilings of this type are very cost effective, as they provide a simple way to conceal many of the necessary building materials, such as pipes, wires, etc., from plain sight in a room, while allowing easy access for maintenance purposes.
The erection of a suspended ceiling requires the installation of a metal framework grid in which the individual ceiling tiles are positioned. This grid, which uses a series of inverted T-bars which interlock to form rectangular openings configured to hold the ceiling panels, must be carefully installed before the tiles can be inserted in place. Installation of this frame can be a tedious process, as it is usually affixed in some manner to the ceiling joints or other appropriate overhead structure, and requires careful and accurate positioning over the entire area of the room in which the suspended ceiling is to be hung.
U.S. Pat. No. 3,767,008, which issued on Oct. 23, 1973, to LeBlanc et al., describes a suspension ceiling erection method and a support assembly employed therein. The assembly includes a mobile scaffold having several vertically extending sleeves which support an I-beam. The assembly is moved along in the room and adjusted to the desired position to install the metal framework. It states that using this device effects a considerable increase in the efficiency and speed with which suspended ceiling installations may be made.
Although the device taught in the LeBlanc et al. patent does improve on the manner in which suspended ceilings were previously installed, the device is very large and bulky, and requires considerable assembly and disassembly for use. In addition, it requires such space for storage between uses.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a novel apparatus for use in installing suspended ceilings which is small in size, lightweight, and very simple to use.
It is also an object of the present invention to provide an apparatus which has minimal moving parts and can be easily installed.
It is a further object of the present invention to provide a device by which a person can easily install a suspended ceiling by himself.
These and other objects of the present invention are accomplished by a novel apparatus comprising a pair of spaced apart parallel members each of which contain a groove which are aligned, and attachment means for easy mounting to a ceiling beam, whereby a section of framework grid can be inserted into the grooves while it is fastened in the proper position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the apparatus of the present invention;
FIG. 2 is a front elevational view of the apparatus of FIG. 1;
FIG. 3 is a side elevational view of the apparatus of FIG. 1; and
FIG. 4 is a front elevational view of the apparatus of FIG. 1 being used to aid in the installation of the gridwork used to support a suspended ceiling.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1-3, there is shown a device for assisting in the installation of suspended ceilings, generally indicated at 10. Device 10 is preferably an H-shaped apparatus which consists of a pair of essentially parallel arms 12a and 12b which are connected by a section 14 which is located between, and perpendicular to, parallel arms 12a and 12b. Section 14 may contain an aperture 16 which is formed through section 14. Aperture 16 is sized such that a level indicating means 18, such as a bubble level, can be positioned within aperture 16. Ideally, level indicating means 18 can be viewed from either side of device 10.
At one end of device 10, arms 12a and 12b contains a series of grooves, generally indicated at 20. Grooves 20 are shown in the present embodiment as a series of groove pairs 20a, 20b, 20c, and 20d. As can be seen most clearly in FIG. 2, the grooves in pair 20a are aligned with each other; this is also shown for pairs 20b, 20c, and 20d. In the present embodiment, grooves 20 are spaced at one-inch intervals. The purpose of grooves 20 will be apparent hereinafter.
On the inside wall of arm 12b at the end opposite grooves 20 are formed several raised protrusions 22, while at the end of arm 12a opposite grooves 20 there is a threaded aperture 24. A clamp 26 is threadingly engaged within aperture 24 such that surface 26a of clamp 26 travels between arms 12a and 12b. Clamp 26 also contains a T-handle 26b for ease of operation.
Finally, arms 12a and 12b are each provided with an axial bore 28 at the end containing grooves 20, while at the opposite end, arms 12a and 12b terminate at an approximate 45 degree angle to the axis of arms 12a and 12b (as is best seen in FIG. 2), creating an angular surface 30 on each arm. Bores 28 could be used to attach another device 10 to the bottom of the first by the use of dowels or similar means, thus providing an additional set of grooves 20 if the ceiling is to be suspended at a lower height than possible using device 10.
FIG. 4 illustrates the use of device 10 in the installation of the framework for use in hanging a suspended ceiling. Device 10 is secured to a ceiling joist 40 by locating joist 40 between arms 12a and 12b and adjusting clamp 26 by turning T-handle 26b until joist 40 is firmly held between surface 26a and protrusions 22. A piece of gridwork 42, which is in the shape of an inverted T, is positioned firmly within one of the pairs of grooves 20a, 20b, 20c, or 20d located on arms 12a and 12b. Device 10 can also be used to install L-shaped angle iron gridwork which is used along the walls when installing a suspended ceiling. Depending on the length of gridwork 42, it may be helpful to use a second device 10 attached to another joist 40 at some distance away from device 10 along the length of gridwork piece 42. Gridwork piece 42 can then be accurately located at the proper distance from the floor by adjusting the position of device 10 using clamp 26, or by using a different set of grooves 20. When the proper distance is located, gridpiece 40 can be adjusted for levelness by observing level indicating means 16, and then clamp 26 retightened. Piece 40 can then be permanently fastened in place using any conventional means. This process is then repeated until the complete framework for supporting the suspended ceiling is installed.
There are many advantages to using the novel device of the present invention. First, this device makes it possible for a single person to easily install a suspended ceiling by himself. Also, as the device has a series of parallel grooves for supporting the gridwork, there is greater flexibility in the positioning of the gridwork. Finally, the angled ends of the device may be used as a convenient guide for the miter cutting of inside and outside angles for the exterior walls during the installation.
While this invention has been shown and described in terms of a preferred embodiment thereof, it will be understood that this invention is not limited to this particular embodiment and that many changes and modifications may be made without departing from the true spirit and scope of the invention as defined in the appended claims.
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An apparatus for use in installing the framework for supporting a suspended ceiling having a pair of parallel legs for supporting a section of gridwork and a clamp for attaching the apparatus to a ceiling joist. The apparatus includes a plurality of grid supporting positions as well as level indicating means to accurately position the suspended ceiling supports.
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TECHNICAL FIELD
[0001] The present invention relates to a disinfection method and a disinfection device.
BACKGROUND ART
[0002] It has been well known that catechins have disinfection action. This action is ascribed to the ability of the catechins to generate hydrogen peroxide by reducing the dissolved oxygen, which in turn exerts disinfection action (see, for example, Non-Patent Literature 1). In addition, among various catechins, those possessing gallate groups such as epigallocatechin, epicatechin gallate, and epigallocatechin gallate, have higher affinity to cell membrane and thus are known to have stronger disinfection action (see, for example, Non-Patent literature 2 or 3).
CITATION LIST
Non-Patent Literature
[0000]
Non-Patent Literature 1: H. Arakawa, M. Maeda, S. Okubo and T. Shimamura, “Role of Hydrogen Peroxide in Bactericidal Action of Catechin”, Biol. Pharm. Bull., 2004, 27, 3, p. 277-281
Non-Patent Literature 2: H. Ikigai, T. Nakae, Y. Hara, T. Shimamura, “Bactericidal catechins damage the lipid bilayer”, Biochimica et Biophysica Acta, 1993, 1147, p. 132-136
Non-Patent Literature 3: K. Kajiya, S. Kumazawa, and T. Nakayama, “Membrane action and anti-bacterial activity of catechin derivatives from tea”, Foods & Food Ingredients Journal of Japan, 2004, 209, p. 834-838
SUMMARY OF INVENTION
Technical Problem
[0006] As disclosed in Non-Patent literatures 1 to 3, catechins exhibit disinfection action and exert its disinfection effect even at a low concentration. However, in order to achieve sufficient disinfection effect, an extended reaction time of 12 hours or more was required.
[0007] The present invention is devised by focusing on this problem, and aims at providing a disinfection method and a disinfection device, that can achieve a high disinfection effect within a short period of time.
Solution to Problem
[0008] In order to achieve the above stated object, the disinfection method according to the present invention comprises the steps of: bringing a disinfecting agent containing catechins into contact with an item to be disinfected, and irradiating the disinfection agent with light.
[0009] The disinfection method according to the present invention achieves its disinfection effect by the mechanism described below. As shown in FIG. 1 , catechins exert disinfection action by reducing the dissolved oxygen (O 2 ) and generating hydrogen peroxide (H 2 O 2 ). When the hydrogen peroxide is irradiated with light, hydroxyl radicals (.OH) are generated through the photolysis of the hydrogen peroxide, as shown in FIG. 2 . Since catechins possess a high antioxidative effect, it may be usually considered that its phenolic hydroxyl group acts as a donor of e − and H + , while also functioning to extinguish hydroxyl radicals, so as not to produce the disinfection effect.
[0010] However, as shown in FIG. 2 , the phenolic hydroxyl group, after acting as the donor, eventually assumes quinone structure, and cannot extinguish the hydroxyl radicals. For this reason, in the presence of abundant dissolved oxygen, phenolic hydroxyl group acts as a donor and does not extinguish hydroxyl radicals, thereby achieving the disinfection effect mediated by hydroxyl radicals.
[0000] The inventors of the present invention, as discussed above, discovered an unexpected disinfection effect using a method that usually is not associated with having any disinfection effect, thus arriving at the present invention.
[0011] According to the disinfection method of the present invention, hydroxyl radicals can be generated by irradiating the disinfecting agent with light after bringing the disinfecting agent containing catechins in contact with the item to be disinfected. Disinfecting effect by hydroxyl radicals can thus be obtained so that the item to be disinfected is disinfected. Hydroxyl radicals thus generated achieves higher disinfecting effect in a shorter period of time compared to the disinfecting effect of catechins observed without light irradiation.
[0012] Catechins are more stable and less toxic compared to hydrogen peroxide, therefore, compared to the disinfecting method directly utilizing hydrogen peroxide, one can obtain more stable as well as safer disinfecting effect. In the disinfection method according to the present invention, any method can be used in terms of ways of bringing the disinfecting agent in contact with the item to be disinfected, including the method in which the disinfecting agent is applied or sprayed and the method in which the item to be disinfected is submerged in a solution containing the disinfecting agent.
[0013] In the disinfection method according to the present invention, catechins such as catechin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, gallocatechin, catechin gallate, and gallocatechin gallate may be used alone, or in combinations of more than two kinds, or in a form in which one or two kinds or more are polymerized in multitude (for example, proanthocyanidin). However, catechins that have gallate groups are especially preferable. Catechins having gallate groups exhibit higher affinity to cell membrane and exert higher disinfecting effect on the subject of disinfection that has cell membrane. Furthermore, in comparison with the catechins not having gallate groups, catechins having gallate groups generate more hydrogen peroxide by reducing the dissolved oxygen, so that the amount of hydroxyl radicals generated by light irradiation also increases, thereby further improving the disinfecting effect.
[0014] In the disinfection method according to the present invention, the disinfecting agent may comprise only catechins or may also contain other substances. Other substances may be any substances including water, disinfecting agent, saccharide, coloring agent, fragrance agent, seasoning, synthetic or natural disinfecting agent. The disinfecting agent other than catechins includes strongly acidic water, iodine preparation (such as iodine tincture, povidone-iodine and the like), chlorides (such as sodium hypochlorite and the like), mercurochrome solution, chlorhexidine gluconate, acrinol, alcohols (such as ethyl alcohol) and hydrogen peroxide solution. However, substances that are safe are more preferable.
[0015] The disinfecting agent containing catechins preferably comprises a solution containing the catechins, and more preferably comprises aqueous proanthocyanidin solution. Furthermore, the aqueous proanthocyanidin solution preferably has a proanthocyanidin concentration of 0.25 to 4 mg/mL. Proanthocyanidin is a substance in which multiple catechins are polymerized. As such, it can provide high disinfecting effect with superior safety.
[0016] In the disinfection method according to the present invention, the light can be of any wavelength such as ultraviolet light or infrared light, as long as it can generate hydroxyl radicals from hydrogen peroxide, however, the wavelength of 350 nm to 500 nm is more preferable. In this case also, high disinfecting effect as well as high safety can be achieved. Especially, safety can further be improved if visible light is used.
[0017] The irradiance of the irradiation light is preferably no less than 300 mW/cm 2 or more, and larger the irradiance, more effective is the light.
[0018] The disinfection device according to the present invention is characterized by comprising a disinfecting agent comprising an aqueous proanthocyanidin solution having the proanthocyanidin concentration of 0.25 to 4 mg/mL, and light emitting means provided to be capable of irradiating the disinfecting agent that is in contact with an item to be disinfected with light having a wavelength of 350 to 500 nm.
[0019] The disinfection device according to the present invention can suitably execute the disinfection method according to the present invention. According to the disinfection device of the present invention, hydroxyl radicals can be generated by bringing the disinfecting agent in contact with the item to be disinfected, followed by irradiating the disinfecting agent with the light using light emitting means for emitting the light. Accordingly, this achieves the high disinfecting effect due to proanthocyanidin and leads to the disinfection of the object to be disinfected. Furthermore, proanthocyanidin has low toxicity and therefore is very safe.
[0020] In the disinfection method and disinfection device according to the present invention, the light emitting means can be of any type, for example, incandescent lamp, fluorescent lamp, halogen lamp, xenon lamp, LED (light emitting diode), semiconductor laser, or those utilizing sun light. The irradiated light can be single wavelength light, light containing multiple wavelengths, or light containing a prescribed band of wavelengths.
[0021] The disinfecting agent that utilizes light concerning the present invention is characterized by containing an aqueous proanthocyanidin solution, and further characterized by having the proanthocyanidin concentration of 0.25 to 4 mg/mL.
[0022] The disinfecting agent that utilizes light concerning the present invention is suitably used as the disinfecting agent in the disinfection method and the disinfection device concerning the present invention. The disinfecting agent of the present invention is used by applying or spraying on the item to be disinfected. Subsequent irradiation of light generates hydroxyl radicals, and the item to be disinfected is disinfected by the action of the hydroxyl radicals. Furthermore, proanthocyanidin has low toxicity, therefore, is highly safe.
[0023] The disinfection method and the disinfection device according to the present invention, as well as the disinfecting agent that utilizes light concerning the present invention, are preferably, suitably selected depending on the item to be disinfected. For example, if the item to be disinfected is comprised of tooth or dentures in oral cavity, the disinfecting agent preferably constitutes tooth paste, mouth wash, or rinsing agent for dental treatment and the like.
Advantageous Effects of Invention
[0024] According to the present invention, a disinfection method and a disinfection device that can achieve a high disinfection effect in a short period of time, are able to be provided.
BRIEF DESCRIPTION OF DRAWINGS
[0025] FIG. 1 is a reaction formula explaining the principle of anti-bacterial activity of catechins.
[0026] FIG. 2 is a structural formula and a reaction formula depicting the principle of hydroxyl radical generation in catechins and the change in the phenolic hydroxide group.
[0027] FIG. 3 is an ESR spectrum when a mixed sample containing proanthocyanidin and DMPO is irradiated with light in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0028] FIG. 4 is a graph showing the effect of proanthocyanidin concentration with respect to the amount of oxygen radical generated in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0029] FIG. 5 is a graph showing the effect of the duration of laser irradiation with respect to the amount of oxygen radical generated in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0030] FIG. 6 is a graph showing the hydroxyl radical extinguishing activity of proanthocyanidin in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0031] FIG. 7 is a graph showing the superoxide extinguishing activity of proanthocyanidin in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0032] FIG. 8 is a graph showing the disinfecting effect of proanthocyanidin and laser irradiation in the disinfection method and the disinfection device according to the embodiment of the present invention.
[0033] FIG. 9 is a graph showing changes in the disinfecting effect by different concentrations of proanthocyanidin in the disinfection method and the disinfection device according to the embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0034] Hereinafter, description will be given for the disinfection method and the disinfection device of the present invention.
[0035] The disinfection method and the disinfecting agent of the disinfection device of the present invention comprise an aqueous proanthocyanidin solution, light emitting means for irradiating the disinfecting agent with light comprises a semiconductor laser capable of irradiating with light having the wavelength of 405 nm.
[0036] In regard to the disinfection method and the disinfection device, tests were performed to examine their characteristics and effects as Examples.
EXAMPLES
Example 1
[0037] First of all, a qualitative and quantitative analysis of the oxygen radical species generated by light irradiation to proanthocyanidin was performed. The qualitative and quantitative analysis of the oxygen radicals was performed by the Electron Spin Resonance (ESR) spin trapping method. As the spin trapping agent, 5,5-dimethyl-1-pyrrolidone N-oxide (DMPO; from Labotec Co., Ltd.) was used.
[0038] In order to examine the effect of a proanthocyanidin concentration with respect to the amount of oxygen radicals generated, 150 μL of aqueous proanthocyanidin solution (from Indina Japan Co., Ltd.) and 150 μL of DMPO were mixed in a microplate (96 wells) such that the final concentration of proanthocyanidin became 0 to 4 mg/mL and that of DMPO became 300 mM. The samples in the wells were irradiated with a 405 nm laser light at the output of 300 mW (irradiance of 940 mW/cm 2 ) for 60 seconds and ESR measurements were made using an ESR device (product name: JES-FA-100, from JEOL Ltd.).
[0039] The conditions for the ESR measurements were as follows.
field sweep: 330.50-340.50 mT field modulation frequency: 100 kHz field modulation width: 0.05 mT amplitude: 80 sweep time: 2 min time constant: 0.03 s microwave frequency: 9.420 GHz microwave power: 4 mW
[0048] Obtained ESR spectrum is shown in FIG. 3 . Amounts of respective oxygen radicals generated were obtained as relative intensity to a signal obtained from a manganese marker that is installed in the ESR device. Results are shown in FIG. 4 . In addition, in order to examine the effect of the duration of laser irradiation with respect to the amount of oxygen radicals generated, further ESR analysis was performed with a fixed concentration of proanthocyanidin (PA) of 4 mg/mL, and durations of laser irradiation ranging from 0 to 120 seconds, while other conditions were kept unchanged. The results are shown in FIG. 5 .
[0049] As shown in FIG. 3 , a hyperfine structure constant of obtained ESR spectrum was analyzed and qualitative analysis was performed. As the result, by irradiating proanthocyanidin with light, formation of DMPO-OH (spin trapping of hydroxyl radical) and DMPO-OOH (spin trapping of superoxide) were confirmed.
[0050] As shown in FIG. 4 , signal intensities of DMPO-OH and DMPO-OOH increased up to the proanthocyanidin concentration of 1 mg/mL, however, the signal intensity became saturated above that concentration. In addition, as shown in FIG. 5 , it was confirmed that the duration of laser irradiation has hardly any effect on the formation of DMPO-OH and DMPO-OOH. This is likely due to the fact that the reaction of forming DMPO-OH and DMPO-OOH by the hydroxyl radicals and super oxides generated from proanthocyanidin is in equilibrium with the reaction of extinguishing the hydroxyl radicals and superoxides by the excess proanthocyanidin.
Example 2
[0051] Following experiment was performed in order to evaluate the ability of proanthocyanidin to extinguish oxygen radicals. The amount of hydroxyl radicals generated by ultrasonic scission of water, extinguished by the addition of proanthocyanidin was examined. An ultrasonic wave generator having the frequency of 1650 kHz and output of 30 W was used for ultrasonic wave irradiation. 100 μL of aqueous proanthocyanidin solution and 100 μL of DMPO were mixed in a glass test tube such that the final concentration of proanthocyanidin became 0 to 64 mg/mL and that of DMPO became 150 mM. After mixing, the samples were immediately set to an ultrasonic wave generator and irradiated with ultrasonic wave for 30 seconds. Subsequently, ESR measurements were made. The conditions for ESR measurements were identical to those used in Example 1. The results of the measurements are shown in FIG. 6 .
[0052] In addition, the ability of proanthocyanidin to extinguish superoxide was evaluated. Superoxide was generated by the hypoxanthine/xanthine oxidase reaction system. 50 μL of hypoxanthine, 30 μL of dimethylsulfoxide, 50 μL of aqueous proanthocyanidin solution, 20 μL of DMPO and 50 μL of xanthine oxidase were mixed in this order, such that the final concentration of hypoxanthine was 500 μM, that of proanthocyanidin was 0 to 1 mg/mL, that of DMPO was 300 mM, and that of xanthine oxidase was 0.1 U/mL. After the addition of xanthine oxidase, the samples were mixed for seconds, and subjected to ESR measurements. The conditions for ESR measurements were identical to those used in Example 1. The results of the measurements are shown in FIG. 7 .
[0053] As shown in FIG. 6 , 30 seconds of ultrasonic scission of water produced about 15 μM of hydroxyl radicals. Addition of proanthocyanidin to the reaction system suppressed the formation of DMPO-OH in a concentration dependent manner. At the concentration of about 60 mg/mL of proanthocyanidin, it was confirmed that DMPO-OH was not at all formed. The IC 50 (median inhibitory concentration) of proanthocyanidin against DMPO-OH generation was 1.5 mg/mL.
[0054] In addition, as shown in FIG. 7 , DMPO-OOH was generated about 3.5 WI when proanthocyanidin was not added. Addition of proanthocyanidin to the reaction system decreased the formation of DMPO-OOH in a concentration dependent manner. At the concentration of about 0.25 mg/mL of proanthocyanidin, it was confirmed that DMPO-OOH was not formed. The IC 50 of proanthocyanidin against DMPO-OOH generation was 0.005 mg/mL.
Example 3
[0055] Disinfection test was carried out to examine the disinfecting effect of the disinfection method and the disinfection device according to the embodiment of the present invention. As the bacteria, Streptococcus aureus ATCC 25923 was used, and subjected to the test as a suspension in physiological saline solution at 2×10 7 cells/mL. 150 μl of bacteria suspension and 150 μL of proanthocyanidin was mixed in a microplate and irradiated with 405 nm laser at 300 mW (irradiance of 940 mW/cm 2 ) for 10 minutes.
[0056] The effect of concentration with respect to the disinfecting effect was examined by making the final concentrations of proanthocyanidin 4 μg/mL to 3.2 mg/mL. After the irradiation, 50 μL of the sample and 50 μL of 5000 U/mL catalase were mixed to stop the reaction of hydrogen peroxide derived from proanthocyanidin. Subsequently, series of 10 times dilutions were prepared and inoculated on Brain Heart Infusion (BHI) agar medium, cultured at 37° C. for 24 hours under the aerobic condition, and the disinfecting effect was determined. As the controls, the disinfecting effects of proanthocyanidin alone (1 mg/mL) and laser irradiation alone were also evaluated.
[0057] The test results obtained with proanthocyanidine concentration of 1 mg/mL with or without the laser irradiation, and those with neither proanthocyanidin nor laser irradiation are shown in FIG. 8 . In addition, the test results obtained by performing laser irradiation while changing the proanthocyanidin concentrations are shown in FIG. 9 .
[0058] As shown in FIG. 8 , S. aureus used in the test was confirmed to be hardly disinfected by proanthocyanidin alone. In addition, as shown in FIG. 9 , S. aureus was also found to be hardly disinfected by 10 minutes of laser irradiation alone. Whereas, disinfecting effect was observed when a sample in which bacteria and proanthocyanidin were mixed was irradiated with laser. Especially, the highest disinfecting effect of 99% or more was observed when the proanthocyanidin concentration was 0.25 to 4 mg/mL.
[0059] It was further confirmed that when the concentration of proanthocyanidin was either lower than 0.25 mg/mL or higher than 4 mg/mL, the disinfecting effect was attenuated. High disinfecting effect was only observed within a limited range of concentrations, most likely, due to the relation between the disinfecting effect of hydroxyl radicals generated by irradiating proanthocyanidin with laser and the anti-oxidative action of excess proanthocyanidin. In other words, when the concentration of proanthocyanidin is increased, at first, the catechins contained in the increasing amount of proanthocyanidin reduce the dissolved oxygen and produce hydrogen peroxide which is then photolysed by laser irradiation to generate more hydroxyl radicals, thus increasing disinfecting effect. However, when the concentration of proanthocyanidin becomes high and the amount of dissolved oxygen reduced by catechins becomes low, the excess catechins would extinguish hydroxyl radicals already produced, thereby reducing disinfecting effect. In addition, it is also possible that the darker color of highly concentrated aqueous proanthocyanidin solution absorbed laser light and hindered the reaction from hydrogen peroxide to hydroxyl radicals.
[0060] Thus, according to the embodiment of the disinfection method and the disinfection device of the present invention, the disinfecting effect by the hydroxyl radicals generated by irradiating the disinfecting agent with light can be achieved and be used to disinfect the item to be disinfected. Furthermore, the synergistic effect of the disinfecting effect derived from catechins and the disinfecting effect derived from hydroxyl radicals can be achieved. By the actions of the generated hydroxyl radicals, higher disinfecting effect can be achieved in shorter period of time, compared to the disinfecting effect of catechins without light irradiation. Proanthocyanidin comprising catechins is stabler and less toxic compared to hydrogen peroxide, therefore, in comparison to the disinfection method directly utilizing hydrogen peroxide, the present invention provides stabler disinfecting effect in significantly safer manner.
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A disinfection method, a disinfection device, and a disinfecting agent which utilizes light, which can achieve a high disinfection effect within a short time are provided. A disinfecting agent containing catechins is brought into contact with an item to be disinfected, and then the disinfecting agent is irradiated with light. The disinfecting agent preferably comprises an aqueous proanthocyanidin solution produced by polymerizing multiple catechin molecules each having a gallate group. Particularly, the aqueous proanthocyanidin solution preferably has a proanthocyanidin concentration of 0.25 to 4 mg/mL. Light with which the disinfecting agent is irradiated preferably has a wavelength of 350 to 500 nm.
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BACKGROUND OF THE INVENTION
To regain the full use of the wrist following various types of injuries, it is frequently found necessary or helpful to provide some form of physical therapy. This is especially true if the wrist has been confined for some time in a cast which tends to leave it in a stiff and weakened condition. Muscles associated with the bending or flexing of the wrist become atrophied, and the stiffened or enlarged tissues surrounding the joints interfere with the full motion of the joint system.
A particular form of therapy that is helpful in certain cases involves the controlled application of a force to the hand and wrist in a manner which draws the back of the hand upward toward a fully flexed position. Allowing the wrist to be flexed or bent in this manner tends to restore full freedom of movement while muscular resistance to the applied force restores tone and strength to the muscles.
Heretofore, there has not been available a suitable brace or appliance for such use. Makeshift braces and springs are typically too awkward and cumbersome to be worn under everyday living conditions.
What is needed is a compact, low-profile device that may be worn conveniently under typical conditions of work or recreation. In the provision of such a device, it is also important to insure that the device will not subject the wrist to compression or tension forces that are in some cases harmful to the joint and may only result in additional injury or an extended recovery period.
The present invention is directed toward the provision of a device of this type which may be applied to the wrist of a patient by a physician or physical therapist.
DESCRIPTION OF THE PRIOR ART
Various types of braces and appliances for therapeutic use in treating bone or muscle disorders are described in the prior art.
U.S. Pat. No. 4,409,970 discloses an apparatus and method for the treatment of communited Colles' fracture. The apparatus includes a kit comprising a wire bow, two stainless steel bone screws and an elastic band which are employed to place the fractured joint in traction to promote healing. The apparatus, when assembled, is incorporated into a cast which is formed over it.
U.S. Pat. No. 4,602,620 discloses a "Dynamic Outrigger Extension for Dorsal Wrist Splints" which employs adjustably positioned wheels mounted on a wire frame arranged immediately over the digits of a postoperative hand for precise alignment of dynamic splint forces following implant resection arthroplasty of the metacarpophalangeal joints. Such precise alignment of the digits and joints is essential to assure their proper alignment after healing.
The prior art devices do not address the need for a dynamic splint component with a capability for providing the desired rotational force to the wrist as an aid in restoring full strength and movement to an injured wrist.
SUMMARY OF THE INVENTION
In accordance with the invention claimed, a prefabricated dynamic splint component is provided for use in treating certain wrist conditions or injuries. The device is a compact, low profile structure that is intended to apply a rotational force to the wrist without subjecting the wrist joint to compression or tension.
It is, therefore, an object of the present invention to provide an improved dynamic splint component for use in treating certain types of wrist conditions or injuries.
Another object of this invention is to provide a dynamic splint component that is intended to be mounted upon the forearm and wrist of a patient for the purpose of applying a perpendicular force to the back of the hand, thereby to draw the hand upwardly as it flexes the wrist.
A further object of this invention is to provide a dynamic splint component which, in the process of applying such a flexing or torquing force to the wrist is constrained by virtue of its form and construction from applying compressive or tractive forces to the wrist structure.
A still further object of this invention is to provide a dynamic splint component in a form which may be readily applied to the forearm and wrist of a patient by a physician or physical therapist using commonly available splinting materials such as thermo plastics.
A still further object of this invention is to provide with such a dynamic splinting component a convenient and effective means for mounting the splinting component to the forearm and wrist of the patient.
Yet another object of this invention is to provide such a dynamic splinting component in a compact and low profile form so that it will not seriously interfere with the normal use of the hand and wrist of the patient.
Further objects and advantages of this invention will become apparent as the following description proceeds, and the features of novelty which characterize the invention will be pointed out with particularity in the claims annexed to and forming a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily described with reference to the accompanying drawings, in which:
FIG. 1 is a perspective view showing the dynamic splint component of the invention secured to the wrist, forearm and hand of a patient;
FIG. 2 is a perspective view showing the prefabricated structure of the dynamic splint component;
FIG. 3 is a cross-sectional view of the structure of FIG. 2 as seen along line 3--3;
FIG. 4 is an enlarged view showing a member of the structure of FIG. 2 herein identified as the distal wire frame;
FIG. 5 is a cross-sectional view showing the construction of the portion of the distal wire frame enclosed in circular area 5 of FIG. 4;
FIG. 6 is a cross-sectional view of the structure of FIGS. 2 and 3 as seen along line 6--6 of FIG. 3;
FIG. 7 is a perspective view showing an alternate construction of the prefabricated structure of FIGS. 1-6;
FIGS. 8 and 9 illustrate sequential steps in the fabrication and preparation of the forearm and wrist gauntlet to which the prefabricated splint component is to be secured;
FIGS. 10 and 11 illustrate sequential steps in the preparation of the palmar sling by means of which the splint component applies a flexing force to the hand and wrist of the patient;
FIG. 12 shows the forearm and wrist gauntlet secured to the forearm and wrist of a patient;
FIG. 13 shows an enlarged view of the proximal hook as it is secured to the gauntlet, the hook being shown also in FIGS. 9 and 12 inside the areas enclosed by the circle 13 in both figures; and
FIG. 14 illustrates the method by which the proper placement of the splint component upon the gauntlet is determined for the marking of mounting holes at the underside of the gauntlet.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to the drawings by characters of reference, FIGS. 1-6 disclose a dynamic splint component 10 embodying the invention and comprising a U-shaped or wishbone frame 11, left and right pivotal arms 14 and 15, distal wire frame 16 and tension band 17. Associated with component 10 and working in cooperation therewith upon the forearm, wrist and hand 18 of the patient are wrist gauntlet 21 and palmar sling 22.
In a first implementation of the invention, the wishbone frame 11 comprises a two-part metal structure in which a narrow metal strip 23 serves as the proximal leg of the wishbone and a specially formed U-shaped member 24 forms the two distal arms of the wishbone.
Strip 23 is approximately four and one-half inches long, one-half inch in width and one-eighth of an inch in thickness. The distal end of strip 23 is bent downward to form a one-eighth of an inch perpendicular projection 25 which is used for securing strip 23 to member 24. Holes 26 in strip 23 are provided, one near each of the proximal and distal ends of the strip for use in securing component 10 to a gauntlet 21. An additional hole 27 is provided adjacent projection 25 for use in securing strip 23 to member 24.
Member 24 is formed from a U-shaped stamping in which the legs of the "U" are approximately one and one-half inches long and are tilted slightly outwardly. The base of the "U" is approximately four inches in length. The width of the stamping is one-half inch and its thickness is one-eighth of an inch. The final form of member 24 is then obtained by placing the stamping on a horizontal surface and bending each of the two legs of the "U" upwardly through an angle of ninety degrees. The bends are made just inboard of the base of the legs at right angles to the base of the "U", as shown most clearly in FIG. 2.
As shown in FIGS. 2 and 3, member 24 is secured to the end of strip 23 by aligning hole 27 of strip 23 with a clearance hole 28 at the center of member 24. A screw 29 is then passed through hole 28 and threaded into hole 27. Projection 25 of strip 23 now wraps around the edge of member 24 preventing rotation of members 23 and 24, relative to each other.
The two pivotal arms 14 and 15 of the distal wire frame 16 are identical. Each is made from a two inch length of quarter inch outer-diameter hollow tubing. A bend 30 of approximately forty degrees is made at a point one-half inch from a first end 31 of the length of the tubing. One-quarter inch inboard from each end of the tubing, a hole 32 is drilled and tapped for a small screw such as an AWG #6 screw. The axes of the two holes are parallel with the axis of bend 30.
Distal wire frame 16 is made from a ten and one-half inch length of three-thirty-seconds of an inch diameter stiff wire. Both ends of the wire are bent towards each other in a common plane. One bend forms an inside angle of approximately 75 degrees at a point approximately three and one-quarter inches inboard from a first end 33; the other bend forms an inside angle of approximately 105 degrees at a point approximately two and one-quarter inches inboard from a second end 34 of the distal wire frame 16. The end segments 35 of the wire that are outboard from the two bends are parallel with each other and a line 36 joining the ends 33 and 34 is perpendicular with the two end segments 35. As shown in FIG. 4, the angles thus formed are intended to yield a configuration for the distal frame 16 such that when the end segments 35 are aligned with the longitudinal axis of the forearm and wrist, a center segment 37 of frame 16 will be aligned approximately with the palmar crease of hand 18 of the patient.
As shown in FIGS. 4 and 5, two tubular rings 39 and 41 are mounted on the center segment 37 of distal wire frame 16, the wire having been passed through the rings prior to the formation of the second bend. The inside diameter of the rings is sufficiently larger than the outside diameter of the wire to accommodate a nylon tie cord 42. Each of rings 39 and 41 may be locked into a desired position along segment 37 by means of a set screw 43 that turns into a threaded hole in the wall of the rings.
Assembly of the splint component 10 proceeds as follows: Strip 23 is first attached to member 24 as already described. The pivotal arms 14 and 15 are next pivotally secured to the ends of the two distal arms of member 24 as shown in FIGS. 2, 3 and 6 wherein a screw 44 is shown passing through a washer 45, a clearance hole in the end of the distal arm of member 24, a second washer 46 and is finally threaded into hole 32 at end 31 of each of pivotal arm 14 or 15. In the final step of the assembly operation, ends 33 and 34 of distal frame 16 are inserted into the free ends of the pivotal arms 14 and 15, and are secured therein by means of set screws 47 that are turned into holes 32 adjacent the free ends of arms 14 and 15.
The dynamic splint component 10 is intended to be supplied to physicians and physical therapists in the form as just described. The physician or therapist then mounts component 10 to the wrist, forearm and hand of the patient as shown in FIG. 1, using methods and materials yet to be described in the present disclosure.
As shown in FIG. 1, frame 11 is secured to the underside of wrist gauntlet 21 with strip 23 thereof directed rearwardly toward the patient's elbow and with the distal arms of member 24 curving upwardly and forwardly toward the dorsum of the hand. Arms 14 and 15 slope downwardly from their pivotal attachments at screws 44, then upwardly beyond bends 30. With proper positioning of the component 10, central segment 37 of frame 16 passes over the central portion of the dorsum of the hand 18, as shown in FIGS. 1 and 4, and the pivotal joint of component 10 is aligned with the center of rotation of the wrist for upward and downward movement of the hand. Component 10 is secured in this position to the wrist gauntlet 21 in a procedure to be described later. The hand sling 22 is then secured to frame 16 using two nylon ties 42, one at each side of the hand. Each of the ties passes through a hole at the edges of the hand sling 22 and through one of the rings 39 or 41 of frame 16. Rings 39 and 41 are then positioned to fit the hand and are secured by means of the set screws 43. Tension band 17 is then secured at one end to the center segment 37 of frame 16 and at the other end to a hook 51. Hook 51 is secured to the top side of the proximal end of gauntlet 21.
Band 17 is selected to provide the desired amount of force to frame 16. As shown in FIG. 1, frame 16 to which sling 22 is secured can only move rotationally with arms 14 and 15 about their pivotal mountings at screws 44. The only component of force that is applied to the hand is thus a perpendicular force directed upwardly from the dorsum of the hand, the perpendicular force urging rotation about screws 44.
FIG. 1 shows tension force 52 produced by band 17 as having a perpendicular component 53 and a longitudinal or compression component 54. The perpendicular component 53 is applied to the hand and wrist, while the splint component 10 supports the longitudinal component 54, so that no compression force is applied to the wrist of the user.
FIG. 7 shows a second embodiment of the invention in the form of a splint component 10'. Component 10' is nearly identical with component 10, except that it is designed to be secured to the dorsal or top side of the wrist and forearm rather than to the underside. This mounting arrangement, as shown in FIG. 7, is accommodated by turning frame 11 upside down relative to its position shown in FIG. 1, and reversing the angles of distal arms 14 and 15. With these changes, pivotal screw 44 is again aligned with the wrist joint and arms 14 and 15 together with frame 16 are again directed toward the desired position over the dorsum of the hand.
It should be recognized that either components 10 or 10' of FIGS. 1 and 7 may be mounted on the arm of a user below the wrist, as shown in dash lines in FIG. 7, to bias the hand in a downward direction and still fall within the scope of this invention.
The forming of wrist gauntlet 21 is illustrated in FIGS. 8 and 9. Gauntlet 21 may be made from any of the various splinting or casting materials such as a low temperature thermoplastic material. In the case of a thermoplastic material, a sheet of the material is first heated to a temperature at which it is pliable and easily cut and formed. The heated thermoplastic material 55 is then cut to the shape and dimensions relative to the wrist and forearm, as shown in FIG. 8, with a longitudinal (relative to the forearm) dimension 56 of approximately six inches and a lateral dimension 57 of approximately twelve inches. Gauntlet 21 is then formed by wrapping material 55 about the wrist and forearm with ends 58 and 59 overlapping on the top or dorsal side of the wrist and forearm. Appropriate ties 61, such as Velcro® fasteners, are added to secure the gauntlet in position upon the wrist. The forming and construction of gauntlet 21 is completed by the addition of hook 51 which is secured to the top side of the gauntlet at its proximal end. As shown in FIGS. 9, 12 and 13, hook 51 may be formed from a length of wire with the center of the wire forming the hook, and the ends of the wire folded back upon themselves to form anchoring extensions 63 forward and aft of the hook. The hook may then be secured to the gauntlet material using a suitable adhesive tape 64.
Once gauntlet 21 has been formed and prepared for use as just described, it is allowed to cool to room temperature. At room temperature, it stiffens and retains its shape, but is still sufficiently flexible that its overlapping edges may be drawn apart and the gauntlet may then be removed from the wrist and then replaced again some time later.
Palmar sling 22 may be formed from the same type of thermoplastic material, as illustrated in FIGS. 10 and 11. As shown in FIG. 10, the heated thermoplastic material 65 is first cut into a strip approximately two inches wide and six inches long. In FIG. 11, material 65 has been formed to fit the contours of the palm of the hand, its ends extending at both sides of the hand and folded upwardly toward the dorsum. Holes are provided at both upwardly extending edges to receive nylon cords 42 which are to be held by rings 39 and 41 of distal frame 16. When sling 22 is formed in this manner to a particular patient's hand, it will retain its custom-fitted contours as it cools, and will fit the patient's hand comfortably throughout its use.
Gauntlet 21 and sling 22 having been formed as just described, are now positioned and secured upon the patient's forearm and wrist, as shown in FIG. 12. The assembled component 10 is then held in position, and its position adjusted for the desired alignment with the wrist and hand, as shown in FIG. 14. The desired locations of mounting holes 26 in strip 23 of frame 11 are then marked with a pencil on the under surface of gauntlet 21. Gauntlet 21 may then be removed from the patient's forearm so that holes may be punched or drilled at the marked locations. Component 10 is then secured to the underside of gauntlet 21 using screws at holes 26.
Gauntlet 21, with attached component 10, is then remounted upon the patient's wrist, as shown in FIG. 1. With the addition of tension band 17, which is connected between center segment 37 of frame 16 and hook 51, and with the addition of ties 42 which secure the ends of the palmar sling 22 to rings 39 and 41, the mounting of the dynamic splint component 10 is complete.
One feature of component 10, as mounted to the wrist and hand in the manner just described, is that as the hand is moved downward toward a rest position, tension force 52 and its longitudinal component 54 increase, but the perpendicular component 53 decreases toward zero. A rest position is thus afforded in which the hand and wrist are relieved of all external forces with component 10 fully supporting the tension force of band 17. As the hand and wrist are moved upwardly from the rest position and thence downwardly again toward the rest position, the perpendicular component 53 provides the desired restraint against downward rotation of the wrist that is helpful in the healing process.
An effective dynamic splint component is thus provided in accordance with the stated objects of the invention, and although but two embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims.
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A compact, low-profile, prefabricated dynamic splint component for use in treating certain wrist conditions or injuries. The component is mounted on the wrist and forearm by means of a wrist gauntlet. It subjects the hand to a perpendicular force that urges the hand upward about the wrist joint while avoiding the application of any compression forces to the wrist.
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This application is a divisional application of allowed application U.S. Ser. No. 10/293,206 filed Nov. 13, 2002, which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to new derivatives of sulphonamides, with the general formula (I), as well as to their physiologically acceptable salts, the processes for their preparation, their application as medicaments in human and/or veterinary therapy and the pharmaceutical compositions that contain them.
The new compounds object of the present invention can be used in the pharmaceutical industry as intermediates and for preparing medicaments.
BACKGROUND OF THE INVENTION
The superfamily of serotonin receptors (5-HT) includes 7 classes (5-HT 1 -5-HT 7 ) encompassing 14 human subclasses [D. Hoyer, et al., Neuropharmacology, 1997, 36, 419]. The 5-HT 6 receptor is the latest serotonin receptor identified by molecular cloning both in rats [F. J. Monsma, et al., Mol. Pharmacol., 1993, 43, 320; M. Ruat, et al., Biochem. Biophys. Res. Commun., 1993, 193, 268] and in humans [R. Kohen, et al., J. Neurochem., 1996, 66, 47]. Compounds with 5-HT 6 receptor antagonistic activity are useful for the treatment of various disorders of the Central Nervous System and of the gastrointestinal tract, such as irritable intestine syndrome. Compounds with 5-HT 6 receptor antagonistic activity are useful in the treatment of anxiety, depression and cognitive memory disorders [M. Yoshioka, et al., Ann. NY Acad. Sci., 1998, 861, 244; A. Bourson, et al., Br. J. Pharmacol., 1998, 125, 1562; D. C. Rogers, et al., Br. J. Pharmacol. Suppl., 1999, 127, 22P; A. Bourson, et al., J. Pharmacol. Exp. Ther. , 1995, 274, 173; A. J. Sleight, et al., Behav. Brain Res. , 1996, 73, 245; T. A. Branchek, et al., Annu. Rev. Pharmacol. Toxicol., 2000, 40, 319; C. Routledge, et al., Br. J. Pharmacol. , 2000, 130, 1606]. It has been shown that typical and atypical antipsychotic drugs for treating schizophrenia have a high affinity for 5-HT 6 receptors [B. L. Roth, et al., J. Pharmacol. Exp. Ther., 1994, 268, 1403; C. E. Glatt, et al., Mol. Med. , 1995, 1, 398; F. J. Mosma, et al., Mol. Pharmacol., 1993, 43, 320; T. Shinkai, et al., Am. J. Med. Genet., 1999, 88, 120]. Compounds with 5-HT 6 receptor antagonistic activity are useful for treating infant hyperkinesia (ADHD, attention deficit/hyperactivity disorder) [W. D. Hirst, et al., Br. J. Pharmacol. , 2000, 130, 1597; C. Gerard, et al., Brain Research, 1997, 746, 207; M. R. Pranzatelli, Drugs of Today, 1997, 33, 379]. Patent application WO 01/32646 describes sulphonamides derived of bicycles, with 6 members each, aromatic or heteroaromatic with 5-HT 6 receptor antagonistic activity. Patent application EP 0733628 describes sulphonamides derived of indole with an 5-HT 1F receptor antagonistic activity useful for treating migraines. In general, the study of the scientific literature and patents indicates that small structural variations give rise to agonist or antagonist compounds of various receptors of serotonin that are useful for treating different diseases, depending on the receptor for which they show affinity.
After laborious research the inventors have managed to synthesize new compounds with the general formula (I) that show interesting biological properties making them particularly useful for use in human and/or veterinary therapy.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides new compounds with 5-HT 6 serotonin receptor antagonistic activity useful in the preparation of a medicament for prevention or treatment of various disorders of the Central Nervous System, and in particular anxiety, depression, cognitive memory disorders and senile dementia or other dementia processes in which there is a predominant cognition deficit, psychosis, infant hyperkinesia (ADHD, attention deficit/hyperactivity disorder) and other disorders mediated by the 5-HT 6 serotonin receptor in mammals, including man.
The compounds object of the present invention have the general formula (I)
wherein
A represents a substituent selected from among:
A heteroaromatic ring of 5 or 6 members containing 1 or 2 heteroatoms selected from among oxygen, nitrogen and sulphur, optionally substituted by 1 or 2 halogen atoms, by a C 1 –C 4 alkyl radical or by a phenyl or heteroaryl radical with 5 or 6 members containing 1 or 2 atoms of oxygen, nitrogen or sulphur; A bicyclic heteroaromatic ring containing 1 to 3 heteroatoms selected from among oxygen, nitrogen and sulphur, optionally substituted by 1 or 2 halogen atoms or by a C 1 –C 4 alkyl radical: A group selected from among:
R 1 represents hydrogen, a C 1 –C 4 alkyl radical or a benzyl radical;
n represents 0, 1, 2, 3 or 4;
R 2 represents —NR 4 R 5 or a group with formula:
Wherein the dotted line represents an optional chemical bond;
R 3 , R 4 y R 5 independently represent hydrogen or a C 1 –C 4 alkyl; X, Y and Z independently represent hydrogen, fluorine, chlorine, bromine, a C 1 –C 4 alkyl, a C 1 –C 4 , alkoxy, a C 1 –C 4 alkylthio, trifluoromethyl, cyano, nitro and —NR 4 R 5 ; W represents a bond between the two rings, CH 2 , O, S and NR 4 ; m represents 0, 1, 2, 3 or 4; with the condition that when m=0, A is a substituted phenyl;
or one of its physiologically acceptable salts.
The alkyl term C 1 –C 4 represents a linear or branched carbonated chain including 1 to 4 atoms of carbon, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and terc-butyl.
Compounds object of the present invention that correspond to the above formula can be selected from among:
[1] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [2] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [3] Hydrochloride N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [4] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-3,5-dichlorobenzenesulphonamide. [5] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-4-phenylbenzenesulphonamide. [6] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-5-chlorothiophene-2-sulphonamide. [7] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [8] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [9] N-[3-(2-dimethylamino-ethyl)-1H-indol-5-yl]-6-chloroimidazo[2,1-b]thiazol-5-sulphonamide. [10] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [11] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide hydrochloride. [12] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [13] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide hydrochloride. [14] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]-5-chlorothiophene-2-sulphonamide. [15] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]-4-phenylbenzenesulphonamide. [16] N-[3-(1-methylpiperidin-4-yl)-1H-indol-5-yl]quinoline-8-sulphonamide. [17] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-2-sulphonamide. [18] N-[3-(1-methyl-1,2,3,6-tetrahydropyridin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [19] N-[3-(4-methylpiperazin-1-yl)methyl-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [20] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-(2-pyridil)thiophene-2-sulphonamide. [21] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-2,1,3- benzothiadiazol-4-sulphonamide. [22] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]quinoline-8-sulphonamide. [23] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-chloronaphthalene-2-sulphonamide. [24] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-4-phenoxybenzenesulphonamide. [25] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-4-phenylbenzenesulphonamide. [26] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-N-ethyl-naphthalene-2-sulphonamide. [27] N-{3-[2-(morpholin-4-yl)ethyl]-1H-indol-5-yl}-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [28] N-{3-[2-(morpholin-4-yl)ethyl]-1H-indol-5-yl}naphthalene-1-sulphonamide. [29] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-2-sulphonamide. [30] N-[3-dimethylaminomethyl-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [31] N-[3-(2-dipropylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [32] N-[3-(2-dipropylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [33] N-[3-(2-dibutylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [34] N-[3-(2-dibutylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide. [35] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-5-chloronaphthalene-1-sulphonamide. [36] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-trans-styrenesulphonamide. [37] N-[3-(4-methylpiperazin-1-yl)methyl-1H-indol-5-yl]-trans-styrenesulphonamide. [38] N-[3-(octahydroindolizin-7-yl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [39] N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-6-chloroimidazo[2,1-b]thiazol-5-sulphonamide. [40] N-{3-[2-(morpholin-4-yl)ethyl]-1H-indol-5-yl}naphthalene-2-sulphonamide. [41] N-[3-(4-methylpiperazin-1-yl)methyl-1H-indol-5-yl]-α-toluenesulphonamide. [42] N-[3-(3-diethylaminopropyl)-1H-indol-5-yl]naphthalene-2-sulphonamide. [43] N-[3-(3-diethylaminopropyl)-1H-indol-5-yl]-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [44] N-{3-[2-(pyrrolidin-1-yl)ethyl]-1H-indol-5-yl}-5-chloro-3-methylbenzo[b]thiophene-2-sulphonamide. [45] N-{3-[2-(pyrrolidin-1-yl)ethyl]-1H-indol-5-yl}naphthalene-1-sulphonamide. [46] N-{3-[2-(pyrrolidin-1-yl)ethyl]-1H-indol-5-yl}naphthalene-2-sulphonamide. [47] N-[3-(2-dipropylaminoethyl)-1H-indol-5-yl]naphthalene-2-sulphonamide. [48] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-chloronaphthalene-1-sulphonamide. [49] N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]naphthalene-2-sulphonamide. [50] N-{3-[2-(morpholin-4-yl)ethyl]-1H-indol-5-yl}quinoline-8-sulphonamide. [51] N-{3-[2-(morpholin-4-yl)ethyl]-1H-indol-5-yl}-4-phenylbenzenesulphonamide. [52] N-[3-(4-methylpiperazin-1-yl)ethyl-1H-indol-5-yl]naphthalene-2-sulphonamide. [53] N-[3-(4-methylpiperazin-1-yl)ethyl-1H-indol-5-yl]-5-chloronaphthalene-1-sulphonamide.
The present invention also relates to the physiologically acceptable salts of the compounds with the general formula (I), particularly the addition salts of mineral acids such as hydrochloric, hydrobromic, phosphoric, sulphuric, nitric acids, and of organic acids such as citric, maleic, fumaric, tartaric acids or their derivatives, p-toluensulphonic acid, methansulphonic acid, camphorsulphonic acid, etc.
The new derivatives with the general formula (I), wherein R 1 , R 2 , R 3 , R 4 , n and A are as indicated above, can be prepared according to the following methods:
METHOD A
By reacting a compound with the general formula (II) or one of its suitably protected derivatives
wherein A is as indicated previously in the general formula (I) and X is an acceptable salient group including a halogen atom, particularly chlorine;
with a 5-aminoindol with the general formula (III), or one of its suitably protected derivatives;
wherein n, R 1 , R 2 and R 3 are as indicated previously in the general formula (I);
in order to obtain the corresponding sulphonamide and, optionally, eliminating from it the protective groups and/or forming a pharmacologically acceptable salt.
The reaction between the compounds with the general formula (II) and (III) is carried out in the presence of an organic solvent such as an alkyl ether, particularly diethyl ether, or a cycloalkyl, particularly tetrahydrofurane or dioxane, a halogenated organic hydrocarbon, particularly methylene chloride or chloroform, an alcohol, particularly methanol or ethanol, an aprotic dipolar solvent, particularly acetonitryl, pyridine or dimethylformamide, or any other suitable solvent.
The reaction preferably is carried out in the presence of a suitable inorganic base such as hydroxides and carbonates of alkali metals, or in the presence of an organic base, particularly triethylamine or pyridine.
The most suitable reaction temperatures range from 0° C. to ambient temperature, and the reaction time is between 5 minutes and 24 hours.
The resulting sulphonamide can be isolated by evaporating the solvent, adding water and eventually adjusting the pH so that it is obtained as a solid that can be isolated by filtration; or it can be extracted by a solvent immiscible in water such as chloroform and purified by chromatography or recrystallisation from a suitable solvent.
The compounds with the general formula (II) are commercially available or can be prepared according to standard methods or by methods analogous to those described in the literature [E. E. Gilbert, Synthesis, 1969, 1, 3] and the compounds with the general formula (III) can be prepared according to standard methods or by methods analogous to those described in the literature [J. E. Macor, R. Post and K. Ryan, Synt Comm., 1993, 23, 1, 65–72.; J. Guillaume, C. Dumont, J. Laurent and N. Nédélec, Eur. J. Med. Chem., 1987, 22, 33-43; M. L. Saccarello, R. Stradi, Synthesis, 1979, 727].
METHOD B
The compounds with the general formula (I), wherein R 1 , R 2 , R 4 , n and A are as indicated above and R 3 represents a C 1 –C 4 alkyl, can be prepared by alkylation of a compound with the general formula (I), wherein R 1 , R 2 , R 4 , n and A are as indicated above and R 3 represents an atom of hydrogen, with an alkyl halogenide or a dialkyl sulphate.
The reaction preferably is carried out in the presence of a suitable base such as hydroxides and carbonates of alkali metals, metal hydrides, alkoxides such as sodium methoxide or potassium terbutoxide, organometallic compounds such as butyl lithium or terbutyl lithium, in the presence of an organic solvent such as an alkyl ether, particularly diethyl ether, or cycloalkyl, particularly tetrahydrofurane or dioxane, a hydrocarbon, particularly toluene, an alcohol, particularly methanol or ethanol, an aprotic dipolar solvent, particularly acetonitryl, pyridine or dimethylformamide, or any other suitable solvent. The most suitable temperatures are between 0° C. and the boiling point of the solvent, and reaction times are between 1 and 24 hours.
The resulting sulphonamide can be isolated by concentrating the filtrate at reduced pressure, adding water and eventually adjusting the pH so that it is obtained as a solid that can be isolated by filtration, or it can be extracted with a solvent immiscible in water such as chloroform and purified by chromatography or recrystallisation from a suitable solvent.
METHOD C
By condensation of a compound with the general formula (I) wherein R 1 , R 3 , and A are as indicated above, n=0 and R 2 represents an atom of hydrogen, with a suitably substituted 4-piperidone the corresponding compound is obtained with the general formula (I) wherein R 1 , R 3 , and A are as indicated above, n=0 and R 2 represents a suitably substituted 1,2,3,6-tetrahydropyridine-4-yl radical.
The reaction can take place in both an acid and a basic medium, in a suitable solvent at temperatures between 25 and 150° C.
Suitable basic conditions include inorganic bases such as sodium or potassium hydroxide, or organic bases such as pyrrolidine or triethylamine in solvents such as methanol or ethanol. Preferably, solutions of sodium methoxide in methanol at reflux. Reaction times range from 1 to 48 hours.
Suitable acidic conditions include hydrochloric acid in ethanol or trifluoroacetic acid in acetic acid at temperatures between 50 and 100° C. and reaction times ranging from 1 to 48 hours.
The resulting sulphonamide can be isolated by dilution in water, eventually adjusting the pH, to obtain a solid that can be isolated by filtration; or it can be extracted with a solvent immiscible in water such as chloroform and purified by chromatography or by recrystallisation from a suitable solvent.
The compounds with the general formula (I) wherein R 1 , R 3 , and A are as indicated above, n=0 and R 2 represents an atom of hydrogen, can be prepared according to the method A from a 5-aminoindol.
METHOD D
The compounds with the general formula (I) wherein R 1 , R 3 , and A are as indicated above, n=0 and R 2 represents a suitably substituted 4-piperidinyl radical, can be prepared by reducing a compound with the general formula (I) wherein R 1 , R 3 , and A are as indicated above, n=0 and R 2 represents a suitably substituted 1,2,3,6-tetrahydropyridin-4-yl radical prepared according to the method C.
Hydrogenation takes place with the aid of a metallic catalyst such as palladium, platinum or rhodium on a support such as carbon, aluminum oxide or barium sulphate, preferably palladium over carbon, with an initial hydrogen pressure of between 1 and 10 atmospheres, preferably between 2 and 5 atmospheres, in a solvent such as methanol or ethanol. The reaction time ranges from 1 hour to 3 days.
The resulting sulphonamide can be isolated by filtering the catalyst and concentrating the filtrate at reduced pressure. The product recovered can be used as is or it can be purified by chromatography or by recrystallisation from a suitable solvent.
METHOD E
The pharmacologically acceptable salts of compounds with the general formula (I) can be conventionally prepared by reaction with a mineral acid, such as hydrochloric, hydrobromic, phosphoric, sulphuric, nitric acids or with organic acids such as citric, maleic, fumaric, tartaric acids or their derivatives, p-toluensulphonic acid, methansulphonic acid, etc., in a suitable solvent such as methanol, ethanol, ethyl ether, ethyl acetate, acetonitryl or acetone and obtained with the usual techniques of precipitation or crystallisation of the corresponding salts.
During one of the synthesis sequences described, or in the preparation of the sintones used it may be necessary and/or desirable to protect sensitive or reactive groups in some of the molecules employed. This can be performed by means of conventional protective groups such as those described in the literature [Protective groups in Organic Chemistry, ed J. F. W. McOmie, Plenum Press, 1973; T. W. Greene & P. G. M. Wuts, Protective Groups in Organic Chemistry, John Wiley & sons, 1991]. The protective groups can be eliminated in a suitable latter stage by known methods.
The invention provides pharmaceutical compositions that comprise, in addition to an acceptable pharmaceutical excipient, at least one compound with the general formula (I) or one of its physiologically acceptable salts. The invention also relates to the use of a compound with the general formula (I) and its physiologically acceptable salts in the preparation of a medicament having 5-HT 6 serotonin receptor antagonistic activity, useful for preventing or treating various disorders of the Central Nervous System, and particularly anxiety, depression, cognitive memory disorders and senile dementia processes, and other dementias in which predominates a cognition deficit, psychosis, infant hyperkinesia (ADHD, attention deficit/hyperactivity disorder) and other disorders mediated by the 5-HT 6 serotonin receptor in mammals, including man.
The following examples show the preparation of novel compounds according to the invention. Also described in the affinity for the receptor 5HT 6 of serotonin, as well as galenic formulae applicable to the compounds object of the invention. The examples provided below are provided for purposes of illustration only and are in no way meant as a definition of the limits of the invention.
METHOD A
Example 7
Preparation of N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methyl-benzo[b]thiophene-2-sulphonamide.
To a solution of 3.05 g (15 mMol) of 5-amino-3-(2-dimethylaminoethyl)-1H-indol in 100 ml of pyridine is added dropwise at ambient temperature a solution of 4.21 g (15 mMol) of 5-chloro-3-methyl-benzo[b]thiophene-2-sulphonyl chloride in 20 ml of pyridine. The reaction mixture is stirred at ambient temperature for 20 hours. It is then evaporated to dryness, slightly alkalinised with diluted ammonia and dissolved in ethyl acetate. The organic phase is washed with water and a saturated solution of sodium bicarbonate, it is separated and dried with anhydrous sodium sulphate. The organic solution is evaporated to dryness and the resulting solid is repeatedly washed with ethyl ether, to yield 5.5 g (82%) of N-[3-(2-dimethylaminoethyl)-1H-indol-5-yl]-5-chloro-3-methyl-benzo[b]thiophene-2-sulphonamide as a solid with m.p.=226–227° C.
METHOD B
Example 26
Preparation of N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-N-ethyl-naphthalene-2-sulphonamide.
To a mixture of 285 mg (0.7 mMol) of N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-2-sulphonamide (example 17) and 80 mg (0.7 mMol) of potassium t-butoxide in 3 ml of DMSO are stirred for 30 minutes at ambient temperature. Then are added 105 mg (0.7 mMol) of ethyl iodide and left with stirring for 3 hours. Water is added and is extracted with ethyl acetate. The organic solution is evaporated to dryness and the resulting crude is purified by chromatography on silica gel, using as an eluent mixtures of methylene chloride/methanol/ammonia, yielding N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]-N-ethyl-naphthalene-2-sulphonamide as a solid with m.p.=49–50° C.
METHOD C
Example 18
Preparation of N-[3-(1-methyl-1,2,3,6-tetrahydropyridin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide.
To a solution of 712 mg (13.2 mMol) of sodium methoxide in 100 ml of methanol are added 850 mg (2.64 mMol) of N-[1H-indol-5-yl]naphthalene-1-sulphonamide followed by 596 mg (5.28 mMol) of 1-methyl-4-piperidone and the resulting solution is heated to reflux for 48 hours. The reaction mixture is concentrated at reduced pressure and the residue obtained is purified by chromatography over silica gel, using as eluent mixtures of methylene chloride/methanol/ammonia, to yield 573 mg (52%) of N-[3-(1-methyl-1,2,3,6-tetrahydropyridin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide as a solid with m.p.=244–245° C.
METHOD D
Example 12
Preparation of N-[3-(1-methyl-piperidin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide.
To a solution of 417 mg (1 mMol) of N-[3-(1-methyl-1,2,3,6-tetrahydropyridin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide in 50 ml of methanol are added 100 mg of 5% palladium on carbon. The mixture is hydrogenated at ambient temperature at an initial hydrogen pressure of 3 atmospheres for 20 hours. The reaction mixture is filtered and the filtrate is concentrated at reduced pressure to provide a crude that is suspended in ethyl ether, yielding 272 mg (65%) of N-[3-(1-methyl-piperidin-4-yl)-1H-indol-5-yl]naphthalene-1-sulphonamide as a solid with m.p.=254–256° C.
METHOD E
Example 3
Preparation of N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide hydrochloride.
1.05 g (2.5 mMol) of N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide (example 2) are dissolved in 10 ml of ethanol and 0.6 ml are added of a 4.2 N solution of hydrochloric acid in ethanol. It is allowed to crystallise at ambient temperature. N-[3-(2-diethylaminoethyl)-1H-indol-5-yl]naphthalene-1-sulphonamide hydrochloride is obtained as a solid with m.p.=255–257° C.
The melting point and spectroscopic data for identifying some of the compounds object of the present invention are shown in the following table:
m.p. Ex R 1 R 2 n R 3 A Salt ° C. IR cm −1 1 H-RMN (300 MHz), δ (solvent) 1 H (CH 3 CH 2 ) 2 N— 2 H — 170–173 3387, 2970,2931, 1466,1236, 1158,1107, 1080,993,862, 805,657, 565. 0.88(t, 6H, J=7.1Hz); 2.28(s, 3H);2.30–2.46(m, 6H); 2.58(m, 2H);6.85(dd, 1H, J=8.6, 2.0Hz); 7.10(m,2H); 7.20(d, 1H, J=8.6Hz); 7.50(dd,1H, J=8.7, 2.0Hz); 7.90(d, 1H, J=2.0Hz); 7.98(d, 1H, J=8.7Hz); 10.10(bb,1H); 10.80(s, 1H). (DMSO-d6) 2 H (CH 3 CH 2 ) 2 N— 2 H — 170 3451, 3337,2972, 1466,1319, 1237,1157, 1132,1091, 991,770, 675,583, 481. 0.90(t, 6H, J=7.1Hz); 2.33–2.55(m,8H); 6.69(dd, 1H, J=8.7, 1.8Hz); 6.95(s, 1H); 7.02(d, 1H, J=1.8Hz);7.05(d, 1H, J=8.7Hz); 7.47(t, 1H,J=7.7Hz); 7.63(m, 1H); 7.70(m, 1H);8.01(m, 2H); 8.12(d, 1H, J=7.5Hz);8.77(d, 1H, J=8.1Hz); 10.10(bb, 1H);10.66(s, 1H)(DMSO-d6) 3 H (CH 3 CH 2 ) 2 N— 2 H HCl 255–257 3378, 3065,2558, 2489,1460, 1317,1162, 1143,1131, 811,687,602, 588. 1.22(t, 6H, J=7.2Hz); 2.91–3.18(m,8H); 6.65(d, 1H, J=8.6Hz); 7.08(d, 1H,J=8.6Hz); 7.17(s, 1H); 7.20(d, 1H,J=1.8Hz); 7.54(t, 1H, J=7.8Hz);7.63(m, 1H); 7.70(m, 1H); 8.03(d, 1H,J=7.8Hz); 8.08(d, 1H, J=7.1Hz);8.14(d, 1H, J=8.2Hz); 8.79(d, 1H,J=8.4Hz); 10.26(s, 1H); 10.90(bb,1H); 11.01(s, 1H). (DMSO-d6) 4 H (CH 3 CH 2 ) 2 N— 2 H — 168–170 3309, 3047,2974, 1566,1467, 1235,1167, 1143,1116, 1001,910,799, 672,687. 0.95(t, 6H, J=7.1Hz); 2.44–2.58(m,6H); 2.66(m, 2H); 6.79(dd, 1H, J=8.6,1.7Hz); 7.08(d, 1H, J=0.9Hz); 7.13(d,1H, J=1.7Hz); 7.23(d, 1H, J=8.6Hz);7.58(m, 2H); 7.87(m, 1H); 9.95(bb,1H); 10.82(s, 1H). (DMSO-d6) 5 H (CH 3 CH 2 ) 2 N— 2 H — 161–163 3387, 2971,1323, 1157,1095, 765,670, 590 0.89(t, 6H, J=7.1Hz); 2.32–2.55(m,6H); 2.62(m, 2H); 6.85(d, 1H, J=8.6Hz); 7.08(d, 1H, J=2.0Hz); 7.13(s,1H); 7.18(d, 1H, J=8.6Hz); 7.33–7.50(m, 3H); 7.64(d, 2H, J=7.5Hz);7.72(sys AB, 2H, J=8.6Hz); 7.78(sysAB, 2H, J=8.6Hz); 9.80(bb, 1H);10.75(s, 1H). (DMSO-d6) 6 H (CH 3 CH 2 ) 2 N— 2 H — 180–181 3375, 2978,1467, 1417,1236, 1212,1115, 994,624. 0.96(t, 6H, J=7.1Hz); 2.52(m, 4H);2.57(m, 2H); 2.66(m, 2H); 6.83(dd, 1H,J=8.6, 1.9Hz); 7.11(d, 1H, J=4.0Hz);7.14(d, 1H, J=1.9Hz); 7.17(d, 1H,J=1.9Hz); 7.20–7.24(m, 2H); 10.01(bb,1H); 1.81(s, 1H). (DMSO-d6) 7 H (CH 3 ) 2 N— 2 H — 226–227 3422, 3238,1332, 1155,1114, 1079,986, 861,803,655, 564. 2.04(s, 6H); 2.23(m, 2H); 2.28(s, 3H),2.59(m, 2H); 6.83(dd, 1H, J=8.4, 1.5Hz); 7.09(s, 2H); 7.19(d, 1H, J=8.4Hz); 7.49(dd, 1H, J=8.7, 1.6Hz);7.91(d, 1H, J=1.6Hz); 7.99(d, 1H,J=8.7Hz); 10.13(bb, 1H), 10.79(s,1H) (DMSO-d6) 8 H (CH 3 ) 2 N— 2 H — 203–205 3357, 1475,1282, 1157,1127, 990,957, 809,773, 613,587, 557,498. 2.09(s, 6H); 2.21(m, 2H); 2.54(m, 2H);6.69(dd, 1H, J=8.6, 1.7Hz); 6.94(s,1H); 7.03(s, 1H); 7.06(d, 1H, J=8.1Hz); 7.49(t, 1H, J=7.8Hz); 7.64(m,1H); 7.71(m, 1H); 8.02(m, 2H); 8.13(d,1H, J=8.1Hz); 8.79(d, 1H, J=8.4Hz);10.10(bb, 1H); 10.68(s, 1H)(DMSO-d6) 9 H (CH 3 ) 2 N— 2 H — 215(desc) 3247, 3094,1467, 1272,1261, 1230,625 2.17(s, 6H); 2.36(m, 2H); 2.65(m, 2H);6.77(dd, J=8.6, 1.7Hz, 1H); 7.07(s,1H); 7.09(s, 1H); 7.18(d, J=8.6Hz, 1H);7.51(d, J=4.5Hz, 1H); 7.81(d,J=4.5Hz, 1H);10.80(s, 1H). (DMSO-d6). 10 H 0 H — 250(desc) 3407, 2390,1466, 1334,1156, 113,1080, 651,565. 1.53–1.80(m, 4H); 2.26(s, 3H); 2.39–2.71(m, 6H); 3.02(d, 2H, J=8.8Hz);6.76(d, 1H, J=8.8Hz); 7.05(s, 1H);7.11(s, 1H); 7.19(d, 1H, J=8.8Hz);7.51(d, 1H, J=8.7Hz); 7.91(s, 1H);8.00(d, 1H, J=8.7Hz); 10.10(bb, 1H);10.90(s, 1H). (DMSO-d6) 11 H 0 H HCl 220(desc) 3423, 3214,3043, 2942,2688, 1464,1317, 1149,1114, 1080,748, 670,646 1.75–1.92(m, 4H); 2.31(s, 3H); 2.66(s,3H); 2.80(m, 1H); 2.95(m, 2H); 3.24(d,2H, J=11.4Hz); 6.76(d, 1H, J=8.7Hz);7.07(s, 1H); 7.19(m, 2H); 7.50(d, 1H,J=8.6Hz); 7.93(s, 1Hz); 8.01(d, 1H,J=8.6Hz); 8.34(s, 1H); 10.90(bb, 1H);11.01(s, 1H). (DMSO-d6) 12 H 0 H — 254–256 3343, 2938,2929, 14701154, 1121,1108, 988,947, 805,769, 589. 1.49(m, 2H); 1.61(m, 2H); 2.14(m, 2H);2.30(s, 3H); 2.40(m, 1H); 2.90(d, 2H,J=10.6Hz); 6.65(d, 1H, J=8.6Hz);6.90(s, 1H); 6.96(s, 1H); 7.05(d, 1H,J=8.6Hz); 7.46(dt, 1H, J=7.51, 1.83Hz);7.64(m, 1H); 7.71(m, 1H); 7.99(d, 1H,J=8.6Hz); 8.03(d, 1H, J=8.6Hz);8.12(d, 1H, J=8.2Hz); 8.77(d, 1H,J=8.6Hz); 10.07(bb, 1H); 10.71(s,1H). (DMSO-d6) 13 H 0 H HCl 212(desc) 3423, 3269,3114, 2955,2733, 1469,1321, 1155,1133, 947,769. 1.80(m, 4H); 2.74(m, 4H); 3.04(m, 2H);3.39(m, 2H); 6.63(d, 1H, J=8.6Hz);7.00(s, 2H); 7.08(d, 1H, J=8.6Hz);7.49(t, 1H, J=7.7Hz); 7.60–7.77(m,2H); 8.04(d, 2H, J=7.5Hz);8.13(d, 1H, J=8.2Hz); 8.79(d, 1H,J=8.2Hz); 10.16(s, 1H); 10.66(bb,1H); 10.88(s, 1H). (DMSO-d6) 14 H 0 H — 284(desc) 3371, 2943,1468, 1410,1324, 1148,993, 604. 1.62(m, 2H); 1.78(d, 2H, J=11.7Hz);1.99(m, 2H); 2.18(s, 3H); 2.55(m, 1H);2.84(d, 2H, J=10.6Hz); 6.81(d, 1H,J=8.6Hz); 7.07(s, 1H); 7.13(m 1H);7.16(s, 1H); 7.20–7.26(m, 1H); 9.90(bb, 1H); 10.83(s, 1H). (DMSO-d6) 15 H 0 H — 247–248 3361, 2936,1318, 1155,1095, 767,670, 587. 1.52(s, 2H); 1.67(m, 2H); 1.85(m, 2H)2.08(s, 3H); 2.44(m, 1H); 2.67(d, 2H,10.25Hz); 6.83(d, 1H, J=8.4Hz);7.01(s, 1H); 7.03(s, 1H); 7.19(d, 1H,J=8.4Hz); 7.35–7.50(m, 3H); 7.63–7.73(m, 4H); 7.79(sys AB, 2H, J=7.6Hz);9.71(bb, 1H); 10.76(s, 1H)(DMSO-d6). 16 H 0 H — 280(desc) 3398, 3257,2933, 1161,1143, 789,589. 1.25–1.52(m, 4H); 1.85(m, 2H); 2.18(s,3H); 2.27(m, 1H); 2.74(d, J=11.4Hz,2H); 6.72(dd, J=8.6, 2.0Hz, 1H);6.83(d, J=1.5Hz, 1H); 6.90(d, J=2.0Hz,1H); 7.02(d, J=8.6Hz, 1H);7.57(m, 1H); 7.74(dd, J=8.4, 4.3Hz, 1H);8.12(dd, J=7.3, 1.3Hz, .1H);8.19(dd, J=8.2, 1.3Hz, 1H); 8.52(dd,J=8.4, 1.7Hz, 1H); 9.21(dd, J=4.3, 1.7Hz,1H); 9.36(s, 1H);10.64(s, 1H). (DMSO-d6). 17 H (CH 3 CH 2 ) 2 N— 2 H — 172–173 3199, 2970,2930, 2870,1327, 1153,1130, 1110,1075, 956,676, 658,551, 476. 0.87(t, J=7.1Hz, 6H); 2.39(m, 6H);2.55(m, 2H); ); 6.82(d, J=8.6Hz, 1H);7.05(s, 1H); 7.09(s, 1H); 7.13(d,J=8.6Hz, 1H); 7.60(m, 2H); 7.73(d,J=8.6Hz, 1H); 7.95(d, J=7.9Hz, 1H)8.01(m, 2H); 8.26(s, 1H); 9.86(bb, 1H);10.71(s, 1H). (DMSO-d6). 18 H 0 H — 244–245(desc) 3346, 2943,1474,1283,1261, 1156,1123, 801,771,589, 503. 2.25(s, 3H); 2.31(m, 2H); 2.46(m, 2H);2.90(m, 2H); 5.34(s, 1H); 6.78(dd,J=8.6, 2.0Hz, 1H); 7.09(d, J=1.5Hz, 1H);7.14(d, J=8.6Hz, 1H); 7.25(d,J=2.0Hz, 1H); 7.49(t, J=7.8Hz, 1H);7.66(m, 1H); 7.75(m, 1H); 8.04(m,2H); 8.14(d, J=8.2Hz, 1H); 8.83(d,J=8.6Hz, 1H); 10.14(bb, 1H); 11.03(s,1H). (DMSO-d6). 19 H 1 H — 230(desc) 2796, 1452,1316, 1149,1114, 1080,1001, 810,646, 559. 1.80–2.26(m, 8H); 2.04(s, 3H); 2.30(s,3H); 3.41(s, 2H); 6.89(dd, J=8.6, 1.56Hz,1H); 7.16(s, 1H); 7.22(d, J=8.6Hz1H); 7.29(s, 1H); 7.49(dd, J=8.7, 1.7Hz,1H); 7.90(d, J=1.7Hz, 1H);7.98(d, J=8.7Hz, 1H); 10.13(bb, 1H);10.93(s, 1H). (DMSO-d6). 20 H (CH 3 ) 2 N— 2 H — 209–211 3377,2951, 2798,1469, 1429,1321, 1158,777, 594. 2.05(s, 6H); 2.32(m, 2H); 2.65(m, 2H);6.86(dd, J=8.6, 1.8Hz, 1H); 7.10(d,J=1.8Hz, 1H); 7.18(d, J=1.8Hz, 1H);7.21(d, J=8.6Hz, 1H); 7.32(dd, J=7.5,4.6Hz, 1H); 7.36(d, J=3.9Hz, 1H);7.71(d, J=3.9Hz, 1H); 7.83(m, 1H);7.93(m, 1H); 8.49(d, J=4.6Hz, 1H);9.97(bb, 1H); 10.79(s, 1H). (DMSO-d6). 21 H (CH 3 ) 2 N— 2 H — 192 3321, 2949,1474, 1327,1152, 1138,1104, 981,614. 2.10(s, 6H); 2.21(m, 2H); 2.56(m, 2H);6.72(d, J=8.6Hz, 1H); 6.96(s, 1H);7.03(s, 1H); 7.07(d, J=8.6Hz, 1H);7.70(m, 1H); 8.07(d, J=7.0Hz, 1H);8.29(d, J=8.8Hz, 1H); 10.14(bb, 1H);10.69(s, 1H). (DMSO-d6). 22 H (CH 3 ) 2 N— 2 H — 250(desc) 3252, 2857,1459, 1426,1333, 1161,1144, 789,680, 589. 2.07(s, 6H); 2.16(m, 2H); 2.51(m, 2H);6.73(dd, J=8.6, 1.8Hz, 1H); 6.94(s,1H)6.99(s, 1H); 7.02(d, J=8.6Hz, 1H);7.59(t, J=7.8Hz, 1H); 7.73(dd,J=8.4, 4.1Hz, 1H); 8.18(m, 2H);8.50(dd, J=8.4, 1.5Hz, 1H); 9.20(dd,J=4.1, 1.5Hz, 1H); 9.45(bb, 1H);10.64(s, 1H). (DMSO-d6). 23 H (CH 3 ) 2 N— 2 H — 230–240(desc) 3404, 2944,2918, 2855,1465, 1332,1157, 1140,1080, 650,639, 526. 2.01(s, 6H); 2.18(m, 2H); 2.57(m, 2H);6.81(dd, J=8.6, 1.7Hz, 1H); 7.02(s, 1H); 7.05(d, J=1.7Hz, 1H); 7.15(d,J=8.6Hz, 1H); 7.57(m, 1H); 7.82(d,J=7.5Hz, 1H); 7.91(d, J=8.9Hz, 1H);8.06(d, J=8.2Hz, 1H); 8.29(d, J=8.9Hz,1H); 8.35(s, 1H); 9.94(bb, 1H);10.74(s, 1H). (DMSO-d6). 24 H (CH 3 ) 2 N— 2 H — 152–154 3232, 2862,2827, 2785,1583, 1488,1333, 1248,1155, 1091,755, 693,571, 541. 2.16(s, 6H); 2.37(m, 2H); 2.66(m, 2H);6.80(d, J=8.6Hz, 1H); 6.96–7.12(m, 6H); 7.14–7.25(m, 2H);7.41(m, 2H); 7.64(dd, J=8.5, 1.9Hz, 2H);9.69(bb, 1H); 10.75(s, 1H). (DMSO-d6). 25 H (CH 3 ) 2 N— 2 H — 184–186 3451, 3388,2950, 2775,1466, 1322,1159, 1095,763, 670,591. 2.08(s, 6H); 2.32(m, 2H); 2.64(m, 2H);6.83(dd, J=8.6, 1.9Hz, 1H); 7.08(d,J=2.0Hz, 1H); 7.11(d, J=1.9Hz, 1H);7.17(d, J=8.6Hz, 1H); 7.34–7.50(m,3H); 7.66(d, J=7.5Hz, 2H); 7.72(ABsys, J=8.6Hz, 2H);7.79(AB sys, J=8.6Hz,2H); 9.79(s, 1H); 10.75(s, 1H).(DMSO-d6). 26 H (CH 3 CH 2 ) 2 N— 2 Et — 49–50 3386, 2970,2931, 1474,1337, 1167,1151, 1130,1073, 661,550 0.82(t, J=7.0Hz, 6H); 0.98(t, J=7.0Hz,3H); 2.37(q, J=7.0Hz, 4H); 2.49(m, 2H);2.54(m, 2H); 3.66(q, J=7.1Hz, 2H);6.73(dd, J=8.61, 1.6Hz, 1H); 6.98(s, 1H);7.17(d, J=1.6Hz, 1H); 7.26(d,J=8.61Hz, 1H); 7.56–7.72(m, 3H);7.99–8.11(m, 3H); 8.26(s, 1H);10.97(s, 1H). (DMSO-d6). 27 H 2 H — 200–201 3366, 2951,2816, 1460,1421, 1319,1283, 1157,1114, 1078,865, 651,561 2.25(m ,6H); 2.27(s, 3H); 2.62(t, J=7.9Hz,2H); 3.52(m, 4H); 6.84(d, J=8.2Hz,1H); 7.06(s, 1H); 7.10(s, 1H);7.20(d, J=8.6Hz, 1H); 7.50(d, J=8.6Hz,1H); 7.92(s, 1H); 8.00(d, J=8.6Hz, 1H); 10.13(s, 1H); 10.80(s, 1H).(DMSO-d6) 28 H 2 H — 218–220 3389, 3152,2916, 2819,1466, 1313,1157, 1129,1108, 771,587 2.30(m, 6H); 2.56(m, 2H); 3.56(m, 4H);6.69(d, J=8.4Hz, 1H); 6.93(s, 1H);7.06(m, 2H); 7.48(t, J=7.3Hz, 1H);7.67(m, 2H); 8.02(m, 2H); 8.13(d,J=8.1Hz, 1H); 8.78(d, J=8.1Hz, 1H);10.10(s, 1H); 10.68(s, 1H). (DMSO-d6) 29 H (CH 3 CH 2 ) 2 N— 2 CH 3 — 134–136 2968, 2930,1488, 1329,1159, 1131,1074, 660,550 0.98(t, J=7.1Hz, 6H); 2.55(m, 6H);2.70(m, 2H); 3.67(s, 3H); 6.84(s, 1H);6.93(dd, J=8.6, 2Hz, 1H); 7.10(d,J=8.7Hz, 1H); 7.18(d, J=1.7Hz, 1H);7.26(s, 1H); 7.57(m, 2H); 7.67(dd,J=8.7, 1.8Hz, 1H); 7.84(m, 3H);8.27(d, J=1.7Hz, 1H). (DMSO-d6) 30 H (CH 3 ) 2 N— 1 H — 148–152 3398, 2930,1467, 1158,1113, 1079,861, 803,651, 561 1.89(m, 6H); 2.29(s, 3H); 2.48(s, 2H);6.83(m, 1H); 7.18(m, 3H); 7.50(m, 1H);7.91(m, 1H); 8.00(m, 1H); 10.13(b,1H); 10.92(s, 1H). (DMSO-d6) 31 H (CH 3 CH 2 CH 2 ) 2 N— 2 H — 76–80 3399, 2959,2931, 1466,1159, 1132,802, 770,588 0.82(t, J=6.7Hz, 6H); 1.34(q, J=6.71Hz,4H); 2.31(m, 4H); 2.40(m, 2H);2.52(m, 2H); 6.69(d, J=8.6Hz, 1H);7.04(m, 3H); 7.47(m, 1H); 7.66(m, 2H);8.02(m, 2H); 8.11(d, J=8.1Hz, 1H);8.78(d, J=8.4Hz, 1H); 10.12(s, 1H);10.67(s, 1H). (DMSO-d6) 32 H (CH 3 CH 2 CH 2 ) 2 N— 2 H — 90–95 3406, 2959,2932, 2872,1466, 1157,1079, 861,652, 561 0.80(t, J=7.3Hz, 6H); 1.31(q, J=7.3Hz,4H); 2.26(m, 7H); 2.38(m, 2H);2.56(m, 2H); 6.83(dd, J=8.4, 1.8Hz,1H); 7.08(s, 2H); 7.20(d, J=8.6Hz,1H); 7.50(dd, J=8.6, 2.0Hz, 1H);7.90(d, J=2.0Hz, 1H); 7.99(d, J=8.6Hz,1H); 10.12(b, 1H); 10.79(s, 1H).(DMSO-d6) 33 H (CH 3 CH 2 CH 2 CH 2 ) 2 N— 2 H — 79–80 3398, 2956,2930, 2870,1466, 1158,1080, 862,801,653, 562 0.84(t, J=6.8Hz, 6H); 1.24(m, 8H);2.26(s, 3H); 2.28(m, 4H); 2.39(m, 2H);2.57(m, 2H); 6.82(dd, J=8.6, 1.9Hz,1H); 7.09(d, J=1.8Hz, 2H); 7.18(d,J=8.6Hz, 1H); 7.50(dd, J=8.6, 1.9Hz,1H); 7.89(d, J=1.8Hz, 1H); 7.98(d,J=8.6Hz, 1H); 10.14(b, 1H); 10.78(s,1H). (DMSO-d6) 34 H (CH 3 CH 2 CH 2 CH 2 ) 2 N— 2 H — 111–113 3291, 2955,2926, 2870,1327, 1158,1136, 772,676,611, 585 0.86(t, J=7.0Hz, 6H); 1.29(m, 8H);2.35(m, 4H); 2.41(m, 2H); 2.53(m, 2H);6.67(dd, J=8.5, 1.9Hz, 1H); 7.09(m,3H); 7.48(t, J=7.9Hz, 1H); 7.68(m,2H); 8.01(s, 1H); 8.04(s, 1H); 8.12(d,J=8.2Hz, 1H); 8.78(d, J=8.2Hz, 1H);10.13(s, 1H); 10.67(s, 1H). (DMSO-d6) 35 H (CH 3 CH 2 ) 2 N— 2 H — 154–156 3402, 2978,1471, 1285,1162, 1135,1018, 780,629, 606 0.88(t, J=6.7Hz, 6H); 2.41(m, 6H);2.49(m, 2H); 6.71(d, J=8.1Hz, 1H);6.88(s, 1H); 7.07(m, 2H); 7.66(m, 2H);7.84(d, J=7.0Hz, 1H); 8.09(d, J=7.0Hz,1H); 8.41(d, J=8.2Hz, 1H); 8.79(d,J=8.6Hz, 1H); 10.17(b, 1H); 10.71(s,1H). (DMSO-d6) 36 H (CH 3 CH 2 ) 2 N— 2 H — 125–130 3404, 2972,1473, 1319,1142, 967,745, 541 0.94(t, J=7.1Hz, 6H); 2.50(q, J=7.1Hz,4H); 2.59(m, 2H); 2.68(m, 2H);6.94(dd, J=8.6, 1.8Hz, 1H); 7.26(m,8H); 7.59(m, 2H); 9.54(b, 1H); 10.77(s,1H). (DMSO-d6) 37 H 1 H — 203(desc) 2809, 1340,1150, 746,542 2.06(s, 3H); 2.22(m, 6H); 3.36(m, 2H);3.49(s, 2H); 6.95(dd, J=8.6, 1.8Hz,1H); 7.18(s, 2H); 7.24(m, 2H); 7.37(m,3H); 7.45(d, J=1.8Hz, 1H); 7.61(m,2H); 9.53(s 1H);10.90(s, 1H). (DMSO-d6) 38 H 0 H — 142–144 3413, 2929,1157, 1113,1080, 862,651, 564 1.12(m, 3H); 1.81(m, 9H); 2.22(s, 3H);2.93(m, 2H); 6.84(dd, J=8.5, 1.7Hz,1H); 6.99(s, 1H); 7.03(s, 1H); 7.20(d,J=8.6Hz, 1H); 7.52(dd, J=8.6, 2.0Hz,1H); 7.90(d, J=1.7Hz, 1H); 8.00(d,J=8.6Hz, 1H); 10.01(b, 1H); 10.61(s,1H). (DMSO-d6) 39 H (CH 3 CH 2 ) 2 N— 2 H — 197–198 3338, 1466,1270, 1237,117, 986,626 0.96(t, J=7.1Hz, 6H); 2.53(m, 6H);2.63(m, 2H); 6.78(dd, J=8.5, 1.6Hz,1H); 7.10(s, 2H); 7.18(d, J=8.6Hz,1H); 7.51(d, J=4.6Hz, 1H); 7.80(d,J=4.6Hz, 1H); 10.78(s, 1H). (DMSO-d6) 40 H 2 H — 85–90 3399, 3257,2920, 2855,2814, 1460,1330, 1157,1131, 1113,1074, 659,551, 477 2.27(m, 6H); 2.61(t, J=7.9Hz, 2H);3.52(t, J=4.6Hz, 4H); 6.82(dd, J=8.6,2.0Hz, 1H); 7.06(s, 1H); 7.07(s, 1H);7.15(d, J=8.6Hz, 1H); 7.61(m, 2H);7.74(dd, J=8.8, 1.8Hz, 1H); 7.96(d,J=8.1Hz, 1H); 8.03(m, 2H); 8.27(s,1H); 9.87(s, 1H); 10.74(s, 1H).(DMSO-d6) 41 H 1 H — 99–102 3398, 2934,2806, 1458,1331, 1284,1153, 1127,700, 542 2.11(s, 3H); 2.32(m, 6H); 3.35(m, 2H);3.56(s, 2H); 4.29(s, 2H); 6.98(d, J=8.2Hz,1H); 7.29(m, 7H); 7.53(s, 1H);9.40(s, 2H); 10.94(s, 1H). (DMSO-d6) 42 H (CH 3 CH 2 ) 2 N— 3 H — 128–130 3259, 2973,2939, 28271468, 1332,1159, 1131,1075, 670,555 0.86(t, J=7.0Hz, 6H); 1.51(t, J=6.9Hz,2H); 2.27(t, J=6.9Hz, 2H); 2.35(q,J=7.0Hz, 4H); 2.46(m, 2H); 6.77(d,J=8.6Hz, 1H); 7.00(s, 1H); 7.10(m,2H); 7.60(m, 2H); 7.72(d, J=8.8Hz,1H); 7.95(d, J=7.9Hz, 1H); 8.02(m,2H); 8.26(s, 1H); 9.86(b, 1H); 10.67(s,1H). (DMSO-d6) 43 H (CH 3 CH 2 ) 2 N— 3 H — 156–158 3247, 2969,2938, 1467,1340, 1159,1113, 1080,862, 666,558 0.88(t, J=7.0Hz, 6H); 1.52(m, 2H);2.29(m, 5H); 2.27(q, J=7.0Hz, 4H);2.37(m, 2H); 6.81(dd, J=8.6, 1.5Hz,1H); 7.06(d, J=1.6Hz, 1H); 7.12(d,J=1.5Hz, 1H); 7.18(d, J=8.6Hz, 1H);7.51(dd, J=8.6, 2.0Hz, 1H); ); 7.91(d,J=2.0Hz, 1H); 7.99(d, J=8.6Hz,1H); 10.06(b, 1H); 10.76(s, 1H).(DMSO-d6) 44 H 2 H — 201–203 3386, 2929,1466, 1157,1106, 1080,992, 861,650, 564 1.62(m, 4H); 2.29(s, 3H); 2.30(m, 4H);2.36(m, 2H);2.63(m, 2H); 6.86(d, J=8.6Hz,1H); 7.05(s, 1H); 7.09(s, 1H);7.21(dd, J=8.6, 2.2Hz, 1H); 7.50(dd,J=8.7, 2.0Hz, 1H); 7.92(s, 1H);7.99(dd, J=8.7, 2.2Hz, 1H); 10.10(b,1H); 10.81(s, 1H). (DMSO-d6) 45 H 2 H — 212–214 3354, 2964,2812, 1466,1201, 1157,1124, 808,773, 593, 1.66(m, 4H); 2.36(m, 6H); 2.58(m, 2H);6.71(d, J=8.6Hz, 1H); 6.93(s, 1H);7.02(s, 1H); 7.07(d, J=8.6Hz, 1H);7.48(m, 1H); 7.68(m, 2H); 8.02(dd,J=7.2, 1.2Hz, 2H); 8.12(d, J=8.2Hz,1H); 8.79(d, J=8.6Hz, 1H); 10.10(b,1H); 10.68(s, 1H). (DMSO-d6) 46 H 2 H — 180–182 3375, 2968,2821, 1467,1323, 1313,1146, 1139,1131, 1079,972,654, 549 1.60(m, 4H); 2.26(m, 4H); 2.35(m, 2H);2.61(m, 2H); 6.82(dd, J=8.6, 2.0Hz,1H); 7.05(m, 2H); 7.14(d, J=8.6Hz,1H); 7.61(m, 2H); 7.74(dd, J=8.6, 1.8Hz,1H); 7.95(d, J=7.9Hz, 1H);8.02(m, 2H); 8.27(s, 1H); 9.86(b, 1H);10.72(s, 1H). (DMSO-d6) 47 H (CH 3 CH 2 CH 2 ) 2 N— 2 H — 58–64(desc) 3398, 3255,2958, 2931,2872, 1466,1330, 1156,1130, 1074,659, 551 0.79(t, J=7.3Hz, 6H); 1.31(q, J=7.3Hz,4H); 2.28(t, J=7.3Hz, 4H); 2.42(m,2H); 2.57(m, 2H); 6.80(dd, J=8.6, 1.7Hz,1H); 7.04(d, J=1.7Hz, 1H); 7.12(m,2H); 7.60(m, 2H); 7.72(dd, J=8.6, 1.7Hz,1H); 7.98(m, 3H); 8.25(s, 1H);9.87(b, 1H); 10.70(s, 1H). (DMSO-d6) 48 H (CH 3 ) 2 N— 2 H — 201–203 3369, 1473,1161, 1125,1017, 789,619 2.06(s, 6H); 2.15(t, J=8.2Hz, 2H);2.52(t, J=8.2Hz, 2H); 6.69(d, J=8.7Hz,1H); 6.85(s, 1H); 7.02(s, 1H);7.08(d, J=8.7Hz, 1H); 7.67(m, 2H);7.84(d, J=7.3Hz, 1H); 8.10(d, J=7.3Hz,1H); 8.41(d, J=8.4Hz, 1H); 8.79(d,J=8.7Hz, 1H); 10.15(b, 1H); 10.70(s,1H). (DMSO-d6) 49 H (CH 3 ) 2 N— 2 H — 180–190 3399, 3255,2943, 1466,1330, 1156,1131, 1075,659, 550 2.03(s, 6H); 2.22(t, J=8.2Hz, 2H);2.58(t, J=8.2Hz, 2H); 6.80(d, J=8.4Hz,1H); 7.04(s, 1H); 7.07(s, 1H);7.13(d, J=8.6Hz, 1H); 7.60(m, 2H);7.74(d, J=8.6Hz, 1H); 7.95(d, J=7.7Hz,1H); 8.02(m, 2H); 8.26(s, 1H);9.86(b, 1H); 10.71(s, 1H). (DMSO-d6) 50 H 2 H — 234–235 3400, 3279,2913, 2852,1464, 1420,1315, 1163,1118, 951,592 2.29(m, 6H); 2.54(m, 2H); 3.57(m, 4H);6.72(d, J=8.1Hz, 1H); 7.01(m, 3H);7.60(t, J=7.7Hz, 1H); 7.74(d, J=8.4Hz,1H); 8.19(m, 2H); 8.52(d, J=8.4Hz,1H); 9.21(s, 1H); 9.44(s, 1H);10.65(s, 1H). (DMSO-d6) 51 H 2 H — 225–228 3340, 2857,1479, 1324,1153, 1116,1094, 768,670, 588 2.29(m, 6H); 2.66(m, 2H); 3.47(m, 4H);6.84(d, J=8.6Hz, 1H); 7.07(s, 1H);7.09(s, 1H); 7.18(d, J=8.4Hz, 1H);7.45(m, 3H); 7.70(m, 4H); 7.79(m, 2H);9.79(s, 1H); 10.77(s, 1H). (DMSO-d6) 52 H 2 H — 129–131 3367, 2924,2852, 2799,1465, 1311,1154, 1130,1077, 666,557 1.40–1.60(m, 4H); 1.83(m, 2H); 2.14(s,3H); 2.36(m, 1H); 2.67(d, J=11.2Hz,2H); 6.78(d, J=8.4Hz, 1H); 6.97(s,1H); 7.00(s, 1H); 7.12(d, J=8.6Hz,1H); 7.50– 7.68(m, 2H); 7.73(d, J=9.0Hz,1H); 8.00(m, 3H); 8.23(s, 1H);9.78(b, 1H); 10.71(s, 1H). (DMSO-d6) 53 H 2 H — 246–249 3329, 2940,2916, 1470,1158, 1125,1110, 1015,791, 598 1.35–1.47(m, 4H); 1.86(m, 2H); 2.17(s,3H); 2.28(m, 1H); 2.76(d, J=10.6Hz,2H); 6.68(d, J=8.8Hz, 1H); 6.75(s,1H); 6.94(s, 1H); 7.08(d, J=9.0Hz,1H); 7.60–7.73(m, 2H); 7.85(d, J=7.1Hz,1H); 8.06(d, J=7.1Hz, 1H); 8.40(d,J=7.9Hz, 1H); 8.79(d, J=9.0Hz, 1H);10.20(b, 1H); 10.68(s, 1H). (DMSO-d6)
Biological Assays
Binding with Serotonin Receptor 5HT 6
Cell membranes of HEK-293 cells expressing the 5HT 6 human recombinant receptor were supplied by Receptor Biology. In said membranes the receptor concentration is 2.18 pmol/mg protein and the protein concentration is 9.17 mg/ml. The experimental protocol follows the method of B. L. Roth et al. [B. L. Roth, S. C. Craigo, M. S. Choudhary, A. Uluer, F. J. Monsma, Y. Shen, H. Y. Meltzer, D. R. Sibley: Binding of Typical and Atypical Antipsychotic Agents to 5-Hydroxytryptamine-6 and Hydroxytriptamine-7 Receptors. The Journal of Pharmacology and Experimental Therapeutics , 1994, 268, 1403] with slight changes. The commercial membrane is diluted (1:40 dilution) with the binding buffer: 50 mM Tris-HCl, 10 mM MgCl 2 0.5 mM EDTA (pH 7.4). The radioligand used is [ 3 H]-LSD at a concentration of 2.7 nM with a final volume of 200 μl. incubation is initiated by adding 100 μl of membrane suspension, (≈22.9 μg membrane protein), and is prolonged for 60 minutes at a temperature of 37° C. The incubation is ended by fast filtration in a Brandel Cell Harvester through fiber glass filters made by Schleicher & Schuell GF 3362 pretreated with a solution of polyethylenimine at 0.5%. The filters are washed three times with three milliliters of buffer Tris-HCl 50 mM pH 7.4. The filters are transferred to flasks and 5 ml of Ecoscint H liquid scintillation cocktail are added to each flask. The flasks are allowed to reach equilibrium for several hours before counting with a Wallac Winspectral 1414 scintillation counter. Non-specific binding is determined in the presence of 100 μM of serotonin. Tests were made in triplicate. The inhibition constants (K i , nM) were calculated by non-linear regression analysis using the program EBDA/LIGAND [Munson and Rodbard, Analytical Biochemistry, 1980, 107 220]. The following table shows results indicative of binding for some of the compounds object of the present invention.
TABLE
% Inhibition
Example
10 −6 M
K i (nM)
1
98.1 ± 4.0
0.28
3
96.6 ± 5.2
3.5
4
96.2 ± 0.6
9.3
5
101.2 ± 0.1
1.0
6
97.6 ± 1.8
8.7
7
103.0 ± 7.9
0.13
8
94.5 ± 7.0
0.76
9
96.8 ± 3.7
2.2
11
101.3
0.98
13
98.3
4.7
14
95.7 ± 3.4
24.3
15
97.4 ± 0.8
6.8
16
94.4 ± 8.6
21.2
17
102.0
5.3
The daily doses in human medicine are between 1 milligram and 500 milligrams of product, which can be given in one or more administrations. The compositions are prepared in forms compatible with the administration means used, such as sugar-coated pills, tablets, capsules, suppositories, solutions or suspensions. These compositions are prepared by known methods and comprise between 1 and 60% by weight of the active principle (compound with the general formula 1) and 40 to 99% by weight of a suitable pharmaceutical vehicle compatible with the active principle and the physical form of the composition used. By way of example, the formula of a tablet containing a product of the invention is shown.
Example of formula per tablet:
Example 1
5 mg
Lactose
60 mg
Crystalline cellulose
25 mg
K 90 Povidone
5 mg
Pregelatinised starch
3 mg
Colloidal silicon dioxide
1 mg
Magnesium stearate
1 mg
Total weight per tablet
100 mg
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The present invention relates to new derivatives of sulphonamides, with the general formula (I), as well as to their physiologically acceptable salts, the processes for their preparation, their application as medicaments in human and/or veterinary therapy and the pharmaceutical compositions that contain them
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BACKGROUND OF THE INVENTION
This invention relates to the support of flexible cables and the like leading to a piece of equipment including one or more movable parts so as to minimize undesirable flexing of such cables as well as to avoid undue interference with other components of such equipment. More particularly, the present invention provides a system for supporting a plurality of cables, tubes, and the like leading to X-ray equipment such as an axial tomographic scanner whereby undesirable bending, flexing, and other movement of the cables are essentially prevented.
The use of tomographic scanning to obtain cross-sectional or profile pictures of an object has become quite widespread. This type of X-ray equipment finds particular utility in providing detailed cross-sections of the internal tissue structure of various parts of the human body. As such, this procedure has developed into an extremely useful tool.
A typical axial tomographic scanner comprises essentially a source arranged to direct X-rays or other penetrating radiation through a planar slice of the object to be examined, means to detect such transmitted radiation after it has passed through the object, and mechanism to alternately translate and rotate the source and the detecting means about the object during such examination thereof. To enable such a device to be operated, suitable power cables, other electrical wiring, cooling-water tubes, and the like (all hereinafter generically designated as "cables") must be led on to the device. Because of the alternate or sequential translational and rotational motions to which such device is subjected during use, these cables necessarily undergo a varying degree of bending and flexing which may result not only in damage to the cables themselves but also in interruption of the operation of the device because of the resultant destruction of one part or another thereof. In addition, there is always the necessity, during operation of the device, of minimizing or preventing interference of the cables with the moving and other parts of the same.
Various arrangements have been suggested heretofore to control the degree of such bending and/or flexing of the cables and/or to prevent in so far as possible any interference of the cables with other components of the scanner. In practice, however, these arrangements have not proved entirely satisfactory and leave something to be desired.
BRIEF SUMMARY OF THE INVENTION
It has now been found that these disadvantages of such previously proposed systems can be effectively eliminated by means of the present invention, which provides an arrangement whereby, during operation of a tomographic scanner, the cables are bent or flexed so that the tension and the compression to which they are thereby subjected are substantially equalized and any slack that would otherwise result in such cables during any translational or rotational movement of the scanner is essentially prevented. In this manner the useful life of the cables is markedly increased, and no "loose" cable is present at any time to interfere with the operation of the scanner.
This objective is basically accomplished by providing two separate chain-cable assemblies each carrying a fixed length of the cables leading to the source of the X-rays or other penetrating radiation. One of such assemblies includes a cable-incoming end, which is anchored in place to the vertically arranged frame, the other end being anchored in place to the indexably rotatable plate of the scanner. The other of such assemblies also has one end anchored in place to this plate, the other, cable-outgoing end being anchored in place on the translatable yoke. Associated with and engaging the first assembly is a pair of vertically arranged rotary members, one of which is journalled on the frame and the other of which is journalled in a carriage movable horizontally with respect to such frame whereby, when the plate is indexably rotated, such other rotary member and its carriage are moved so as to take up the slack that would otherwise result in the first assembly. Similarly, associated with and engaging the second assembly is a horizontally arranged rotary member journalled in a carriage movable in parallel with respect to the yoke whereby, when the yoke is translated, such latter rotary member and its carriage are moved so as to take up the slack that would otherwise result in such second assembly.
Advantageously, each chain-cable assembly comprises a pair of parallel roller chains joined by a plurality of linearly spaced tie bars which support and are attached to the cables. At the same time each rotary member comprises a pair of sprockets transversely spaced so as to engage the parallel roller chains of its respective assembly.
Desirably, each anchoring arrangement includes a fixed bracket provided with a pair of apertures with a pin or spindle extending through each aperture. The inner end of each pin is attached to the corresponding end of its respective chain, the outer end being formed with a head or the like; and a suitable spring is associated with each pin between its head and the bracket. In this manner allowance is made for play in each chain-cable assembly.
The resulting scanner represents a tight operating device exhibiting little or no cable wear other than that from ordinary and regular usage.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described in detail in connection with the accompanying drawings, in which:
FIG. 1 represents an exploded schematic perspective view of a tomographic scanner embodying the present invention;
FIG. 2 is an enlarged schematic perspective front view of such scanner, with various parts omitted and with various other parts shown in broken lines;
FIG. 3 is an enlarged schematic perspective rear view of the scanner, again with various parts omitted and with various other parts shown in broken lines;
FIG. 4 is an enlarged perspective view of a chain-cable assembly, with the cables shown in section;
FIG. 5 is an enlarged detailed view of one of the chain-cable assembly anchoring means; and
FIGS. 6A, 6B, and 6C are schematic views on a small scale to show the relative positions of the first chain-cable assembly when the scanner is in its initial position, has been rotated 90°, and has been rotated 180°, respectively.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1, the axial tomographic scanner basically comprises the vertically arranged frame 12, the indexably rotatable plate 14, and the back-and-forth translatable yoke 16. Frame 12 may be stationary or otherwise fixed in position by itself; or it may be mounted on a pair of oppositely disposed uprights 18 (only one of which is shown) by means of oppositely outwardly extending pivot rods 20 (again only one of which is shown). This latter arrangement enables the frame 12 to be slightly pivoted to the front or to the back as may be desired. In such case, of course, means (not shown) is provided to lock the frame in the position that is selected.
Extending from the vertical side walls 22 and 23 of frame 12 are two horizontally disposed cross-pieces 25 and 26, which centrally support the ring 28 provided with the frontwardly protruding flange 30. Rotatably surrounding this flange is the bull gear ring 32, which is attached to the plate 14. Pinion 34 is provided to drive gear ring 32 and is journalled in gear box 36 suitably affixed to cross-piece 26.
The front side of plate 14 is provided with the parallel rails 38 and 39, which slidingly engage corresponding rails (not shown) on the back side of yoke 16. Translational movement of yoke 16 is effected by means of motor 41, which is mounted on gear box 42. Extending vertically from such gear box is the shaft 44, on the lower end of which is mounted pinion 46 for engagement with rack 48 on the front side of yoke 16.
As indicated, plate 14 is provided with a central opening 50, and yoke 16 with a central opening 51. Thus, when the several basic pieces are assembled, the scanner is adapted to receive an object such as a human body that is to be scanned. Scanning is effected by means of X-rays or other penetrating radiation emanating from source 53 and detected by detector 54, with, of course, sequential translation of yoke 16 and indexed rotation of plate 14 by means of pinion 34. Motor 56 is mounted on gear box 36 for effecting such indexing action of pinion 34. To insure that the translational movement of yoke 16 and the indexed rotation of plate 14 occur in the desired sequence, a suitable electronic or other timing control 58 is connected to motors 41 and 56.
In order to operate the scanner, the appropriate cables 59 are led into the device at 60 upwardly onto a chain or belt 61 and then over the vertically arranged rotary members 63 and 64. Chain or belt 61 may be of any suitable type such as a timing belt but preferably comprises a pair of transversely spaced parallel roller chains 66 and 67 joined by a plurality of linearly separated tie bars 69. Similarly, each rotary member 63 and 64 may be of any suitable type such as a pulley (as when chain 61 comprises a timing belt) but preferably comprises a pair of sprockets 70 and 71 transversely spaced so as to engage the spaced roller chains.
A feature of the present construction is that, where the cables are in contact with the chain, the cables are fastened to the chains (as will be described further below) so as to form a chain-cable assembly of fixed length. Two such chain-cable assemblies are provided, one for use in connection with the rotatable indexing of the plate 14 and one for the translational movement of the yoke 16. The purpose in each instance is to prevent any slack that would otherwise be formed in the cables due to such indexing or translational movement, as will become apparent. To accomplish this objective, each end of each chain-cable assembly is fixed in position.
The chain-cable assembly utilized with the plate-indexing operation is anchored at its cable-incoming end to the bracket 73, which is affixed to the frame. The other end of such assembly is anchored to the bracket 75, which is affixed to the plate. Such anchoring may be accomplished in any suitable manner as, for example, the arrangement shown in FIG. 5. In such case the bracket such as bracket 73 is provided with a pair of apertures 77, through each of which a pin or spindle 78 extends. The inner end of each pin is attached to its corresponding roller chain 67 or 66; and its outer end is provided with a head 79, between which and the bracket a spring member 80 is positioned. Such spring member serves to absorb any shock resulting from variations in the sprockets and/or the roller chains.
Rotary member 64 is rotatably mounted on the frame as at 82. On the other hand, rotary member 63 is rotatably mounted on a carriage 84 which is slideably mounted on a pair of horizontal rods 85 supported by the frame. Motor 56, through the medium of gear box 36 and the attached gear box 87, drives timing belt 89 by means of a belt or chain 90. Carriage 84 being attached to timing belt 89 by clamp 91, rotary member 63 is thereby moved along rods 85 in one direction or the other.
Ring 28 is also provided with a plurality of linearly spaced, horizontally positioned fixed rotatably mounted rollers or idlers 93, which may take any appropriate form but which preferably each comprise a pair of idler sprockets spaced so as to engage the spaced roller chains 66 and 67. Advantageously, these idler sprockets are arranged in a circular pattern adjacent the periphery of the frame to facilitate the indexed rotation of the plate.
In operation, then, each time the plate is indexed, rotary member 63 is also moved in the appropriate direction. With both rotary members 63 and 64 in the position shown in FIG. 2, indexed rotation of the plate 14 occurs in a counter-clockwise direction, as indicated in FIG. 1. Because of the simultaneous movement of rotary member 63 to the left (as viewed in FIG. 2), whatever slack that might result from such indexing is completely taken up by the loop formed by the leftward movement of rotary member 63. To be certain that this result is obtained, the timing belt to which carriage 84 is clamped is driven at a velocity corresponding to the linear equivalent of the velocity at which the instant chain-cable assembly is engaged by the rollers or idler sprockets.
The other chain-cable assembly, which is utilized with the yoke-translation operation, is anchored at one end to bracket 95, which is affixed to the frame. The other, cable - outgoing end of such assembly is anchored to the bracket 96, which is affixed to the yoke. This chain-cable assembly engages rotary member 98, which is rotatably mounted on carriage 100 slideably mounted on a pair of rods 102 supported by the plate. Carriage 100 is moved in one direction or the other by engagement of the rack 104 by pinion 106, which is mounted on the upper end of shaft 44. The relationship between rack-pinion 104-106 and rack-pinion 46-48 is such that carriage 100 is driven at a velocity equal to half that of the yoke. Thus, when plate 14 is driven to the right as viewed in FIG. 1, whatever slack that might result from such translation of the plate is completely taken up by the corresponding movement of rotary member 98.
In this manner, then, the cables are prevented from interfering with any other component or part of the scanner. In addition, the tie bars that extend between the spaced roller chains are so configured that the diameters of the various cables supported thereby are all on the pitch line of the spaced sprockets. With such arrangement the tension exerted on the outer half of each cable as it is flexed is equal to the compression exerted on the inner half of such cable so that cable wear is substantially reduced and a much longer cable life is obtained.
In order to provide each chain-cable assembly, each tie bar 69 is equipped with one or more tie straps 108 as shown in FIG. 4. Each such tie strap may hold only one cable such as the X-ray tube cable 110 in place; or it may hold more than one such cable in place, as with the water hose cables 112 and the intermediate ground cable 114. It will be appreciated, of course, that the configuration of the tie bars 69 will be governed basically by the number and/or the size of the cables supported thereby.
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An axial tomographic scanner is provided with two separate chain-cable assemblies each carrying a fixed length of the cables leading to the scanner. One assembly includes a cable-incoming end anchored to the vertically arranged frame, the other end being anchored to the indexable rotatable plate. The other assembly also has one end anchored to this plate, the other, cable-outgoing end being anchored on the translatable yoke. Associated with and engaging each assembly is a translatable rotary member, which, when the plate is indexably rotated or the yoke is translated, is itself, respectively translated and serves to take up the slack that would otherwise form in the respective assembly.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates generally to the documentation and evaluation of real estate investments, and more particularly, to automated real estate loan origination and underwriting processes from initial customer contact to commitment.
[0002] Methods for documentation and evaluation of real estate loan applications are well known in the investment industry, however, the specific sequence of steps directed toward preparation of the substantial necessary documentation and chosen method of analysis of the financial parameters are a matter of choice. For commercial and industrial real estate investment, the volume of supporting documentation and analysis is substantial, as are the dollar amounts and investment risk. Furthermore, consistency of such procedures and expeditious processing is important. To this end, proprietary computer applications have been developed by individual business entities, which automate individual aspects of the loan preparation, evaluation and authorization process.
[0003] In some cases, investment deals are compiled by business entity personnel who may be geographically distant from the central office, and possibly philosophically distant from the entity's investment policy and standards. Equally important, is early scrutiny of certain deal parameters against threshold parameters which serve to exclude potential real estate deals that fall outside the interests of the business entity. Consequently, the cost of compiling pertinent data and executing an appropriate and effective analysis of the data is an important factor. This is especially true for a business entity that conducts such transactions on a routine basis.
[0004] Computer applications directed toward compiling information about real estate property are known. For example, U.S. Pat. No. 5,794,216 describes an application program executed by a computer that includes a database containing multimedia information for each property, including images of the property, and database-stored parameters corresponding to portions of the image. The multimedia information includes market data and images of the property and neighboring circumstances.
[0005] Computer applications directed toward evaluating real estate are also known. For example, U.S. Pat. No. 5,680,305 describes a computer application that provides a method for evaluating real estate for use by a business entity. The application provides for storage of property description data, usage data, such as rental financial history, and other factors. A numerical “utilization indicator” is determined from these parameters, and after further processing, a “score” is developed, which represents a quantitative evaluation of the real estate property.
[0006] U.S. Pat. No. 5,966,699 describes a method for conducting electronic auctions of loan applications. In this method, a computer system connected to the Internet or other network electronically communicates “electronic” loan application forms from a prospective borrower to a loan authorizer, who maintains viable applications in a database, for subsequent electronic communication to one or more loan institutions for quotations.
[0007] Therefore, a data acquisition computer program is required for compiling loan origination information including financial and physical information relating to a specific property and multimedia real estate market information associated with the property, together with a credit request and 20 loan application. The architecture of the computer program needs to be configured so as to provide consistency of processing among a variety of potential users through use of embedded choices, rules and financial models. The application should require only one-time entry of data in a non-linear sequence of data input screens, and should auto-populate documents with input data and generated values wherever appropriate. The system should be capable of electronically communicating loan documents to business entity personnel at any point during the document preparation process.
BRIEF SUMMARY OF THE INVENTION
[0008] The system and method according to the present invention employs a tool in the form of a personal computer application that automates the real estate loan origination and underwriting process for use by a business entity. The method of the present invention includes steps to be followed by one or more members of the business entity, as well as automated processes within the computer application. Some of the method steps are optional, and advantageously, all of the steps can be followed in any sequence.
[0009] While any of the steps of the method could be taken first, logically, and for purposes of description, the first described step of the method of the present invention is the step of storing in the computer application the basics of the real estate loan application, or “deal”, including property location, property metrics, estimated risks, loan terms and other loan and borrower details, by input of such values on one or more input screens. The next series of steps include data entry into a number of subsequent screens, in any order. Some of the subsequent screens test data inputs against pre-stored rules and based on the results of the tests, display information and commentary. The pre-stored rules are defined according to underwriting and pricing guidelines acceptable to the business entity. Other screens auto-populate certain fields with calculated results obtained by analysis of debt and equity data, using known financial models.
[0010] The system makes available to the user a set of computer screens presented in a generally non-linear sequence. The particular sequence of presentation is arranged to be under user control while at the same time, the sequence is also responsive on a real-time basis to the input data. In this way, the sequence of screens displayed for any given deal dynamically vary, depending on data entry.
[0011] Advantageously, in another step of the method, the system makes available to the user word processing-based documents, such as a loan application and credit request, which have been pre-formatted and auto-populated by the system with both input data and calculated data. In the preferred embodiment, the user initiates a one-way link (accomplished automatically by system utilization of known Windows-based, dynamic links) between the application and the word processing application present on the same computer as the system of the present invention.
[0012] For example, in the preferred embodiment, a “Key Metrics” portion arranged to appear within either a credit request or preliminary loan application is generated, in which selected financial data, such as profitability values such as investor rate of return (IRR), return on investment (ROI), net operating income (NOI), loan structure values, and performance calculations, are arranged in a standard format. These documents are available for editing by one or more members of the business entity, for example, by including paragraphs of text commentary and description. These documents become part of the overall loan origination package made available for subsequent evaluation internal to the business entity and quotation by financial institutions.
[0013] The system takes advantage of intranet and Internet connectivity to enable collaborative data input and evaluation among potentially geographically disparate users. Accordingly, in another optional step of the method, a user can instruct the system to initiate a network communication with other members of the business entity regarding a particular loan application. Optionally, the system can be instructed to copy selected data screens to a server storage location and automatically populate an email message with either attached data screens or hyperlinks to the storage location of the data screens.
[0014] Other steps of the method of the present invention include accessing the remaining data input screens of the system. It is expected that an implementation of the present invention includes screens tailored to the needs of the business entity, and therefore specific screens and screen contents will vary, depending on the needs and preferences of the business entity. As a non-limiting example, additional screens include a “Loan” screen for input of loan-related data, a “Cash Flow/Evaluation” screen, which includes various income/expense-related sub-screens, a “Deal Recap” screen, which summarizes the deal, based on all subsisting data, a “Market” screen which provide for input of the results of an analysis of the market associated with the property to be financed, and an “Asset” screen, which provides for input of the physical features of the property. In some cases, the system provides commentary dynamically responsive to the input.
[0015] Also included in the preferred embodiment is an “Execution” screen, which provides for input of subjective information characterizing the borrower in terms such as, for example, property experience, market experience, financial wherewithal, and forecasted reaction to adverse conditions, including specified types of litigation and criminal activity.
[0016] A “Deal Analysis” screen is included, which dynamically adjusts to the input data and calculated values, thereby providing a summary listing of attributes Advantageously, this screen displays in a single location, the rules/guidelines which have been activated as a result of data input. Also included are “Loan Application” and “Credit Request” screens, in which pertinent data is input and organized into final form for processing. An “Execution” screen is included, which provides input of subjective information characterizing the borrower in terms such as, for example, property experience, market experience, financial wherewithal, and forecasted reaction to adverse conditions, including specified types of litigation and criminal activity.
[0017] A work pad screen taking the form of a spreadsheet, is provided for general use. An “Image” screen is provided, in which images captured by known Microsoft Windows-based methods, or the equivalent, can be added, deleted, arranged and reviewed. Typically, imaged maps and photographs of the site are included as input to the Image screen.
[0018] The result of operation of the steps of the system and method of the present invention is the compilation of information that is input, screened and edited by one or more team members having expertise pertinent to individual data types. This compilation includes calculated values obtained by execution of algorithms, i.e., financial models, that analyze debt and equity investments. Also included are multimedia files, such as imaged maps and photographs of the property and surrounding geographic area. This compilation is automatically arranged in any desirable output format, including a loan origination package made available for subsequent evaluation internal to the business entity and, as desired, quotation by financial institutions. Other automated outputs are possible, such as, for example, a loan request.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a simplified block diagram of an overall computing environment including a computer system 10 of the present invention;
[0020] FIG. 2 illustrates an example of a “Screen Deal” input screen for entering basic data, according to the present invention;
[0021] FIG. 3 illustrates an example “Property Cash Flow” input screen, according to the present invention;
[0022] FIG. 4 illustrates an example “Loan” input screen, according to the present invention;
[0023] FIG. 5 illustrates an example “Cash Flow/Valuation” input screen, according to the present invention;
[0024] FIG. 6 illustrates an example “Deal Recap” input screen, according to the present invention;
[0025] FIG. 7 illustrates an example “Asset” input screen, according to the present invention;
[0026] FIG. 8 illustrates an example “Market” input screen, according to the present invention;
[0027] FIG. 9 illustrates an example “Execution” input screen, according to the present invention;
[0028] FIG. 10 illustrates and example “Environmental Issues”, input screen according to the present invention;
[0029] FIG. 11 illustrates an example “Deal Analysis” input screen, according to the present invention;
[0030] FIG. 12 illustrates an example “Loan Application” input screen, according to the present invention;
[0031] FIG. 13 illustrates an example “Images” input screen, according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0032] Embodiments of the present invention include a data acquisition computer program for compiling loan origination information including financial and physical information relating to a specific property and the real estate market associated with the property, together with a credit request and loan application, other outputs as desired, and steps of a method for using the program. The architecture of the computer program, or application, is configured to provide the benefit of consistency of processing among a variety of potential users, in some cases through ample use of embedded menus, from which the user makes an informed selection among fixed choices for a given data field. Rules imbedded within the application and associated with one or more data input fields automatically operate to assist the user in compiling a data conforming to standards and policies of the business entity. Similarly, use of known fixed financial models, although optionally, a choice among models can be provided, further contributes to consistency of loan origination and underwriting. The application is configured so that specific data entries are made only once by the user, leaving to the application the task of populating copies of that input data into other fields, as necessary.
[0033] Importantly, as a result of the non-linear flow of the data input screens, input can be made at the convenience of each user, and is not system-driven. Moreover, emphasis on network-connectivity among users and interested parties, enables conveyance of early (partially complete) versions of a particular compilation of data describing pertinent real estate market demographics, the physical, financial, and usage data relating to a specific real estate property, together with loan and credit applications, collectively referred to as a “deal”, to business entity personnel who, in other loan originating arrangements, might be the last, or nearly the last to review the deal. Such early scrutiny has been shown to be very effective in forestalling deals which fall outside the standards or interests of the business entity. It has been recognized that input from such individuals helps to formulate the initial version of the deal and avoid unnecessary delay resulting from re-writes.
[0034] FIG. 1 is a simplified block diagram of an overall computing environment including a computer system 10 of the present invention, including at least one computer 12 , which preferably is a personal computer, and a plurality of computer applications arranged to operate in computer 12 . Computer system 10 is arranged to cooperatively connect to external data sources 13 over a network. External sources 13 include data sources arranged to make data available upon demand over an intranet ( 14 ), or the Internet ( 15 ), as applicable. Computer 12 is arranged to operate both independently of, and connected to, network 14 , 15 , which optionally, can be an intranet or the Internet. Computer 12 is also arranged to operate a plurality of applications, including at least one desktop application 16 directed to loan origination and underwriting, written in a suitable programming language, such as, for example, the Delphi (trademark of InPrise Corporation) programming language, a spreadsheet application 18 , such as, for example, Excel (trademark of Microsoft Corporation), a word processing application 20 , such as, for example, Word (trademark of Microsoft Corporation), an optional database application 22 , such as, for example, Access (trademark of Microsoft Corporation), an internet browser application 24 , such as, for example Internet Explorer (trademark of Microsoft Corporation), and other applications, as appropriate.
[0035] In an alternative embodiment, a database application running on a central sever is arranged to capture and archive summary information or file copies for general use within the business entity, or to facilitate collaboration. Personal computers 11 suitably network-connected to computer 12 enable other members of the business entity to communicate with the user of computer 12 . In the preferred embodiment, computers 11 and 12 are configured to be interconnected upon demand, via intranet 14 and also by corporate LAN/WAN networks (not shown). Such communication includes electronic mail. Optionally, at least one of personal computers 11 is a server configured and arranged to perform known server functions, including storage of data files, and operation of web-related applications for communicating stored data to users via intranet and internet connections.
[0036] The desktop application 16 is configured and arranged to include local user input 27 , i.e., data entered by a user at the personal computer on which application 16 is running. Local user input 27 is verified against a set of pre-determined input rules 21 resident in application 16 . Input rules 21 are automatically activated by application 16 upon data entry by the user, and are configured to screen input for typographical errors and logical errors. Remote user input 28 , i.e., data communicated over a suitable network from other business entity personnel is communicated to the local user generally in the form of email and optionally, via documents attached to email. The local user transfers this information, as appropriate, as data input 27 to the application. Similarly, the local user accesses commercial sources 29 external to the business entity, and initiates data transfer to application 16 .
[0037] A desirable operating system 26 is Windows (trademark of Microsoft Corporation), OS/2 (trademark of IBM Corporation), or any such other operating system that supports the use of an extended memory, a DLL loading function, and a virtual storage, multi-window GUI environment.
[0038] FIG. 2 illustrates, but not by way of limitation, an example arrangement of a computer input screen 50 for entering basic data pertaining to a request for a loan in connection with a specific real estate property. The example input screen 50 titled “Screen Deal”, is one of a series of input and informational screens comprising the system 10 of present invention. The data input from all of these screens is stored in the database application 22 linked to desktop application 16 . System 10 includes a computational program that is configured to perform arithmetic calculations and comparisons of the input data. The computed results are also stored in the database application 22 . In the preferred embodiment the database application and computational program is a commercially available spreadsheet application 18 .
[0039] System 10 , in the preferred embodiment, is configured and arranged to automatically populate one or more associated spreadsheets by way of a data input and display application including data input screens such as screen 50 and other screens to be described. Also, informational screens are provided, which generally reflect calculated results of data entered into the associated spreadsheet, and may pose summaries, questions or 25 warnings to the user, based on subsisting input data. Return On Investment (ROI), Internal Rate of Return (IRR) and Net Income are displayed at the top of every screen, and represent the deal's (either debt or equity) profitability. These values are constantly updated as the user provides information into the system. In a separate embodiment, system 10 also populates selected input 30 and calculated values into a database associated with a commercially available database application that is dynamically linked with the input and display application, and is a part of, system 10 .
[0040] Screen Deal input screen 50 includes several features that advantageously appear on all screens of the present invention. Generally, included is a display of any set of icons, which, upon user selection using known Windows techniques, direct system 10 to display a corresponding, respective screen. For example, in the preferred embodiment, button icon channels 52 , called “channels” for convenience, are displayed on the left side of screen 50 , which direct system 10 to display screens corresponding to each major screen or suite of screens, described below. As a result, the user can conveniently navigate randomly from any particular screen to any other screen by known Windows navigation techniques.
[0041] Additional features in common with all screens of system 10 include functional pull-down menus 54 , which also are a known feature of Windows applications. These pull-down menus are screen-specific and offer functionality tailored to the currently displayed screen. For example, in the preferred embodiment, the pull-down menus labeled “File”, “Edit”, “Online”, “Activities”, and “Help”, appear at the top of screen 50 .
[0042] Other features in common with all screens of system 10 include guideline warnings representing rule violations, which are displayed throughout the application, as well as being summarized in a “Deal Analysis” channel. Guideline warnings are displayed as appropriate, based on system logic, which responds to both input data as well as calculated values.
[0043] The screens of system 10 optionally are suites of screens corresponding to the channels 52 . For a given channel, a corresponding suite of screens are identified by tab icons 56 near the top of the input area of each screen. These tabs enable the user to switch among members of the suite. Any set of input or informational screens sufficient to display pertinent fields can be included. For example, in the preferred embodiment, Screen Deal suite of screens 50 includes “General Information”, “Programs” and “Property Cash Flow” tabs and corresponding screens, described below. Inclusion of such screens in the design of the system 10 is based both on the need for input data, as well as providing direction to the system, based on the data input. For example, in the preferred embodiment, the “Programs” tab provides a screen that offers a selection of programs to the user, each program being arranged to employ a respective financial model to be used for debt and equity analysis. Moreover, the content and availability of other screens is dynamically determined according to specific data entered on any given screen, as described further, below. This process comprises automatic application of a set of pre-determined rules 23 , stored within application 16 , as data fields are entered.
[0044] FIG. 2 also shows an example “General Information” screen 51 , indicated by a tab 58 of the same name. This screen includes data input fields labeled according to the data type intended for input. Each field is connected to an associated spreadsheet and the input data is made available for subsequent computation, as described below. Specific computations are effected by application of pre-determined computation rules 25 , which are part of application 16 . Although screen 50 can include any number of appropriate input fields describing the property, risk, and loan terms, as understood in the loan origination industry, the preferred embodiment includes general information fields 59 describing the Property Location, Property Type, metrics such as Size and Year Built. For example, one selection of industry-standard input fields relating to risk 60 includes Estimated Risk Values, including Asset Risk, Market Risk, and Execution Risk. Still other input fields relating to loan terms 61 , including requested loan amount, requested term, interest rate type, loan purpose, and purchase price, input fields relating to borrower cash and capital needs. Screen 50 is arranged to display a Calculated Overall Risk Value 63 based on the estimated risk values 61 . Any field, such as “Loan Purpose” 57 , can have an associated pull-down menu of choices, the selection of which results in auto-population of the corresponding input field. Advantageously, restriction to a selection from a fixed menu of choices achieves consistency among users.
[0045] FIG. 3 illustrates an example “Property Cash Flow” arrangement 62 , obtained when the user selects tab 64 labeled “Property Cash Flow” from tabs 56 located near the top of Screen Deal 50 . In the preferred embodiment, inputs made to screen arrangement 62 are incorporated into calculations made by an attached spreadsheet. Icon buttons 70 revealing pop-up worksheets such as, for example, “Average Economic Occupancy Growth”, “Rental Growth” and “Other Growth” are located adjacent pertinent input fields on screen 62 , so that tabular input of growth data corresponding to, for example, six years of experience, can be entered by the user onto respective worksheets, calculated and returned as a calculated result, which is available for manual or optionally, automatic input into the appropriate field in screen 62 . In addition, other economics data input fields 71 include a “Effective Gross Income” value, a “Net Operating Income” value and a “Cash Flow After Reserves” value. In addition, detailed operating expense input fields 72 and tenant improvement costs and leasing commission values are input in screen 62 . Advantageously, a tenant improvement and leasing commission 5 calculator is provided in the form of a pop-up window for the convenience of the user. This calculator provides a window formatted to receive this data, and calculates sums of the data input. Provision is made for input of multiple years of expense values, which are made available for subsequent computation and display, as necessary.
[0046] FIG. 3 also includes a “Programs” tab 73 , the selection of which instructs system 10 to display a screen (not shown) including selectable program options. In instances in which the business entity uses more than one “program” of threshold values for selected parameters, thus screen offers a selection button associated with each program option. Preferably, the choice of options that are displayed is dynamically dependent on subsisting data entered into the application. The user selection of a program results in a respective arrangement of automatically populated values into all pertinent data fields. Each program of thresholds and associated preferences are determined by the business entity.
[0047] FIG. 4 illustrates an example suite of loan screens which are obtained through user selection of icon button channel 74 , labeled “Loans”, from channels 52 , which are visible on every screen presented by system 10 . In the preferred embodiment, selection of “Loan” button 74 instructs system 10 to display the first of the suite of screens, each titled “Loans”, wherein each screen is further identified by a tab including a descriptive sub-title. User selection of the “General Terms” tab 75 instructs system 10 to display the corresponding screen. Optionally, other tabs, which can be selected in any order, indicating additional screens related to “loans”, are displayed near the top of the screen
[0048] Advantageously, if the deal is an equity deal, as determined by selection of “Equity Deal Type” on the General Information screen of the Screen Deal suite of screens, then the suite of loan screens is replaced with a Deal Structure suite of screens (not shown). Deal Structure screens include data input fields characteristic of equity deal types, and are comparable to the 35 suite of loan screens. In addition, the Loan Application and Credit Request suites of screens are also changed to be reflective of the information/structure needs of an equity transaction.
[0049] In the preferred embodiment, with the general terms screen 75 displayed, the user can select from pull-down menus options for “Lien Position” 76 , which includes, for example, selectable fields labeled “First” or “Second Mortgage” or “Equity/Joint Venture”. Advantageously, this fixed assortment of options results in consistent processing by multiple users. Input for “Loan Term” is provided. The user can also select from fixed menu options the “Loan Purpose” 77 , such as “Acquisition”, “Refinance” and 10 “Construction”, as appropriate. Other input fields including “Amortization Schedule” and “Participation” 78 , which includes input fields for “% of Cash Flow”, % of Residual”, and “Minimum Residual Participation”. “Origination and Prepayment Fees and “Rate” input fields 79 and “Prepayment Options” fields 80 , including parameters known in the loan origination industry.
[0050] In one embodiment, the suite of “Loans” screens represented by the General Terms screen 75 , optionally includes other screens (not shown), each accessed by a tab. For example, in FIG. 4 , a “Sources” screen is displayed in which system 10 populates the screen with summary information relating to funding “sources” and corresponding “uses”, in balance-sheet format. Other screens can provide input fields for borrower cash equity, additional collateral, and earnout, as well as input fields relating to senior debt and annual debt service.
[0051] FIG. 5 illustrates an example Cash Flow/Valuation suite of screens, with the “Valuation” screen 81 displayed. “Valuation” screen 81 provides input fields for “Direct Capitalization” values 82 , “Discounted Cash Flow” 83 , and “Sales Comparables” 84 . The default calculations for these values consist of a mixture of user inputs and values driven by the system logic of system 10 . The user has the discretion of overriding both the input and the calculated values, should specific circumstances of the deal so 30 dictate. In the preferred embodiment, in general, data fields associated with capital funding are auto-populated from other inputs to other screens. A “Percent Direct Capital” input field 85 is provided. A pull-down menu of calculation method selections 86 including “Average/Current Proforma NOI”, “Current NOI”, and “Proforma NOI”. In addition, text fields 86 are available for entry of user comments.
[0052] FIG. 5 also shows other tabs representing additional screens included in the suite of Cash Flow/Valuation suite of screens 81 , including tabs 87 labeled “Income By Year”, “Expense By Year”, and “Capital Expenditures By Year”. These screens include data input fields known in the loan origination industry, for example, “Income By Year” includes, for example, net rental income, expense recoveries and other income fields. The remaining screens of the suite include similar known inputs for expense and capital expenditures. Advantageously, in the preferred embodiment, pop-up worksheet screens are available to tally a number of years-average economic opportunity, and various types of income growth, as necessary. The number of years presented dynamically changes based on the loan term. In addition, system 10 trends forward the data input on the Screen Deal—Property Cash Flow screen, based on the growth rates previously assigned by the user.
[0053] FIG. 6 illustrates an example Deal Recap suite of screens, with the deal recap screen 90 displayed. Screen 90 provides an informational display of a “Deal Overview” 91 of the deal in terms of selected values of interest to the business entity. Any selected values can be displayed according to preferences of the business entity. For example, in addition to size and commitment amount, specific calculated underwriting values are displayed. Pricing values are displayed along with return values, including, for example, ROI, net income and IIR. Optionally, the details of these return values and other associated values, as identified by the business entity, are displayed in one or more additional informational screens.
[0054] FIG. 7 illustrates an example suite of “Asset” screens which are obtained through user selection of icon channel 95 , labeled “Asset”, from icon button channels 52 . In the preferred embodiment, selection of “Asset” channel 95 instructs system 10 to display the “Characteristics” screen 96 , indicated by an icon tab of the same name, displayed near the top of the screen. Assets screen 96 includes asset “Description” fields 97 , which include pertinent data fields known in the loan origination industry. Optionally, other input screens providing input fields for additional asset-related fields can be provided as necessary, and identified by selectable icon tabs.
[0055] FIG. 8 illustrates an example suite of “Market” screens which are obtained through user selection of channel 100 , labeled “Markets”, from icon button channels 52 . In the preferred embodiment, selection of “Market” channel 100 instructs system 10 to display a market demand screen 101 labeled “MSA Demand”, which is one of several metropolitan statistical area analysis screens. These screens can be configured to display any number of data input fields pertinent to characterizing market demand. In the preferred embodiment, screen 101 , as shown in FIG. 9 , is arranged in a grid format, in which at the left side is a list of market descriptors 102 , and across the top of the grid are column titles 103 indicating degrees of risk, including, for example, “less risky—1”, “2”, “3”, ‘A”, “5—more risky”, and “not selected”. The user optionally selects, for each listed market descriptor, an icon button from the appropriate column of degrees of risk button icons. A check-mark icon appears as overlaying each selected button. Advantageously, for each position of the Windows pointing device over a button icon, an information window 104 dynamically changes to display both definitions and experience-based information for that particular combination of risk and market descriptor.
[0056] In the preferred embodiment, the market demand screen 101 includes market descriptors such as, for example, number of jobs, employment growth, employment volatility, job diversity, population growth, demographic diversity, business environment, cost of services, defense employment exposure, single employer risk, single industry risk, infrastructure, size of skilled workforce, quality of life.
[0057] Also in the preferred embodiment, the market demand screen 101 includes “User Selected Market Risk” field 105 , which is auto-populated by system 10 with a value developed from previously entered numeric risk data, and a “Calculated Market Risk Rating” field, which is auto-populated by a calculated sum representing the above-described, subjective data indicated by checked grid buttons. Optionally, guideline warnings characterizing the disparity between these two risk rating values are auto-populated in a word processing document. A user, who edits such a document, would thereby have the opportunity to further expand on the reasons surrounding the difference in risk assessment.
[0058] Another metropolitan statistical area (MSA) analysis screen titled, for example, “MSA Supply”, (not shown) includes market descriptors such as, for example, metropolitan statistical area total inventory, metropolitan statistical area total inventory trend, metropolitan statistical area total inventory condition, metropolitan statistical area occupancy, metropolitan statistical area absorption per year, and metropolitan statistical area growth constraints.
[0059] Still another metropolitan statistical area titled, for example “Sub market Demand & Supply”, (not shown) includes market descriptors such as, for example, overall metropolitan statistical area demand, overall metropolitan statistical area supply, overall submarket demand, overall submarket supply.
[0060] FIG. 9 illustrates an example suite of “Execution” screens 200 which are obtained through user selection of channel 201 , labeled “Execution”, from icon button channels 52 . User selection of icon tab 202 , labeled “Borrower” instructs system 10 to display a “Borrower” screen 201 , which includes data input fields 203 which answer the question, “Does the Borrower have the experience to execute the business plan?”. These fields include borrower name, general real estate experience in years, property type experience in years, local market experience in years and number of similar properties owned. Input field grouping 204 includes input fields are intended to answer the question, “Does the Borrower have the financial wherewithal to perform?”, including net worth, liquid assets and empire risks, which includes user-selectable options, including operating shortfalls, highly leveraged, contingent liabilities, and difficulty with lenders.
[0061] A third borrower grouping of input fields 205 are intended to answer the question “How do we expect the Borrower to behave in bad times on their history?” These fields include check-mark icon entries for criminal activity, various civil litigation-related actions, and history with the business entity. Similar questions in connection with the tenant(s) can be provided.
[0062] FIG. 10 illustrates another input screen 66 titled “Environmental Issues” of the Execution suite of screens 200 . Screen 66 lists pre-determined environmental issues 67 arranged as the vertical component of a grid pattern. Across the top of the grid pattern are displayed five column headings 68 , for example, “Not Present”, “Green”, “Yellow”, “Red”, and “Not Selected”, although any suitable set of headings will suffice. Arranged within the grid, beneath the column headings, are icon buttons 69 , which the user selects according to a judgement of the degree of presence of a respective environmental item. Each selection results in the display of an icon checkmark, and mere location of the Windows cursor results in the appearance of explanatory commentary in an information window 55 . Included also, is a text-input window, made available for the user to add comments.
[0063] FIG. 11 illustrates an example of a deal analysis screen 210 , which is obtained through user selection of channel 201 , labeled “Deal Analysis”, from icon button channels 52 . Deal Analysis screen 201 is an informational screen displaying a list 202 of all guideline/rule warnings responsive to data input to-date. This list is a dynamic list drawn from a library of text descriptors each of which characterizes a specific aspect of the deal. For any given deal, the list automatically reflects an analysis of the numeric input data, the system-calculated values, and the non-numeric characterization inputs, e.g. the risk analysis described in connection with other input screens. Advantageously, a display of explanatory text appears in a window 203 , when the user selects each listed characterization. Where appropriate, the text includes context-sensitive data (pertinent to the current deal) embedded within the explanatory text. A questions window 204 is provided, also corresponding to each listed characterization, in which system 10 displays key questions dynamically based on data provided in other input 20 screens.
[0064] FIG. 12 illustrates an example suite of loan application screens 208 which are obtained through user selection of channel 209 , labeled “Loan Application”, from icon button channels 52 . The Loan Application channel 52 instructs system 10 to display the “Borrower Information” screen 210 . Screen 210 includes data fields 211 identifying the borrower, including name, address, entity type, state of organization, along with fields identifying controlling principal(s), and indemnitors. Most, and potentially all of these fields are auto-populated by system 10 , using previously input data. This will depend, of course, on the sequence of input screen selection, and completeness of data entry, as of the selection of the Loan Application channel 209 . Other screens (not shown) optionally included in the Loan Application suite 208 display all information known in the loan origination industry as necessary for comprising a complete loan application. Specific requirements may vary and are typically defined by the business entity. For example, Loan Application screen 210 shows exemplary tabs respectively titled “Property Information” 212 , “Basic Loan Terms” 213 , “Source and Uses” 214 and “Other Terms” 215 , as indicative of such information screens. The data fields of Loan Application screen suite 208 are used by system 10 to automatically generate a loan application suitable for printing or electronic transmission to a loan underwriting entity.
[0065] As indicated in connection with FIG. 4 , which illustrates a suite of loan screens, if the deal type is a debt deal, then the suite of loan application screens shown in FIG. 12 are displayed. If the deal type is an equity deal, as determined by selection of “Equity Deal Type’ on the General Information screen of the Screen Deal suite of screens, then the suite of loan application screens 208 is replaced by a suite Credit Request screens which reflect the information/structural requirements of an equity transaction.
[0066] FIG. 12 shows channel 220 , labeled “Credit Request” among icon button channels 52 , the selection of which instructs system 10 to display a suite of “Credit Request’ screens (not shown). The Credit Request screens include the same information display fields as described in connection with “Loan Application” screen suite 208 . Potentially all of these fields are auto-populated by system 10 , using previously input data, depending on prior completeness of data input. The data fields of Credit Request screens associated with the Credit Request channel 220 are used by system 10 to automatically generate a credit request suitable for printing or electronic transmission to a credit approval entity.
[0067] FIG. 12 also shows, selection of a channel labeled “Work Pad” 222 provides to the user a screen having basic spreadsheet capability, for use as a convenient calculator for incidental calculation.
[0068] FIG. 13 illustrates a channel 224 labeled “Images”, which upon user selection, enables the user to add, insert, and delete images, by selection of buttons 225 , 226 and 227 , respectively. After images are input and arranged in desired sequence, the user can instruct system 10 to sequentially display the images by selecting navigation keys 232 . These images are also moved by system 10 to either the Preliminary or Credit Request word processing documents along with the other deal-related information.
[0069] Referring to any of FIGS. 2-13 , a set of menu choices are displayed at the top of each screen, including standard Windows choices such as “File”, “Edit” and “Help”. In the preferred embodiment, other functionality is also included in the form of menu choices. For example, a menu choice is configured to provide a view of deals grouped by category, such as geographic region, state, or product type (apartment, commercial, etc.). Optionally, system 10 calculates a comparison of any of a group of data fields of interest to the business entity (currently these are “canned reports).
[0070] Advantageously, a copy of the deal recap screen 90 , illustrated in FIG. 6 , is made available on one or more networks, according to the needs of the business entity. Preferably, the copy of screen 90 is made available on the business entity intranet. The copy of screen 90 is created automatically when a user saves for the first time and is then automatically updated on each subsequent save. This functionality requires that the user be connected to the network, for example, an intranet, at the time that the save occurs, and does not require that the user select or otherwise identify or copy the screens. As an automatic function, system 10 copies one or more deal files, for example, the financial model file, the Loan Application file, and the Credit Request file, from the user's hard drive, stores them in a server database in a packaged form suitable for transmission and display over an intranet or optionally, the Internet. The user, through menu selection, instructs the system 10 to automatically populate an email message including a hyperlink to the selected screens, and to automatically send the message to one or more addressees indicated by the user.
[0071] Another optional menu choice is a tracking function, which enables the user to view all posted documents. All data which has been changed over the initial input is graphically highlighted, so that a viewer is able to view the change history by clicking on the data. This information becomes visible in a pop-up window because the data is tagged with at least the revised data author's name, date and time, and old and new value.
[0072] Still other optional menu choices include direct links to web pages providing commercially available market research data and financial reporting data, such as Dunn & Bradstreet (registered trademark). If the user has already provided the postal ZIP Code to system 10 , as part of the property description, such links will automatically route system 10 to data pertinent to the deal.
[0073] Similarly, links to commercial map sources, including orbital images as well as area street maps and aerial photographs are accessed the same way. Copies of such information are obtained by known Windows editing methods.
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A system and method for use by a business entity for loan origination and underwriting in connection with real estate investment using a computer implemented application having a plurality of data input and dialog screens requiring one-time entry of data. The method includes steps to be followed in any sequence by one or more users of the business entity for using the system. The method includes inputting and storing loan origination information via data input screens, the information including financial and physical information relating to a specific real estate investment. The input loan origination information is dynamically compared with pre-determined rules and a dialog screen is displayed on a near real-time basis if any of said rules are violated. The input data is dynamically compared with other rules for determining the ongoing sequence of data input and dialog screens. Comparison with other rules results in the calculation of calculated values and automatically generated dialog text, some of which is automatically populated 15 in word processing documents, an automated loan request and a credit application. The system includes both manual and automatic input of market data quantitatively describing the real estate market associated with the property, as well as multimedia data describing the property and the region surrounding the property. A report representing all of the stored input and calculated values are automatically produced in both paper and electronic form suitable for loan origination and underwriting.
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BACKGROUND OF THE INVENTION
This invention relates to a new and useful improvement in multi-flapper check valves.
In flapper valves of the design disclosed in Bravo, U.S. Pat. No. 1,238,878 (1917), and improved upon by Wheeler in U.S. Pat. Nos. 3,007,488 (1961), 3,026,901 (1962), 3,072,141 (1963), and 3,074,427 (1963), the two flappers are urged toward their seated positions by one or more helical springs wound about a shaft, with the two ends of each spring contacting the two valve flappers respectively. Thus, both flappers are urged toward their seated position by the same spring; or, in the case of multiple spring use, each spring acts upon both flapper elements.
Because of the disparity between the frictional resistances of the two flappers of the check valve of the Wheeler design, and other differences in the forces acting on them, there is a tendency for one of the flappers to close more readily and therefore seat before the other. When one flapper has seated, and the other flapper has almost seated, the energy of a spring acting upon both flappers has been largely dissipated and the torque the spring exerts against the partially open flapper is relatively low. This can cause the flapper to hesitate before closing, resulting in possible pressure surges and hammer.
In Smith, U.S. Pat. No. 3,384,112 (1968), the inventor interconnected the flappers by a relatively complex gearing arrangement to promote synchronous flapper closure. The present invention involves a much less complicated adaptation of the basic valve structure to improve performance. Additionally, the present invention, by proper choice of relative spring strengths, allows for a design in which the flappers close synchronously, or one flapper closes before the other.
For improved valve response, it is desirable to increase the spring torque exerted against each flapper element as the flappers closely approach their seat. Accordingly, it is an object of the present invention to provide a multi-flapper check valve with improved valve response.
Another object of this invention is to provide a multi-flapper check valve wherein total angular spring deflection is reduced.
A further object of this invention is to provide a multi-flapper check valve wherein higher torque springs may be used to increase the torque acting upon a flapper when the flapper is near its seated position.
Yet a further object of this invention is to provide a multi-flapper check valve wherein each flapper is biased by a separate spring.
Other objects and purposes of this invention will appear from the following descriptions, examples, and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the check valve assembly viewed from the downstream side.
FIG. 2 is an axial section of the check valve assembly taken along line 2 -- 2 of FIG. 1.
FIG. 3 illustrates the angular deflection of the torsion spring as used in this novel improvement.
FIG. 4 illustrates the angular deflection of the torsion spring as used in the prior art.
SUMMARY OF THE INVENTION
In this novel improvement in multi-flapper check valves, each flapper is biased by one or more springs not acting on any other flapper. Instead of each of the two legs of the spring acting upon a separate flapper, as is presently commonly done, only one of the legs of each spring acts upon a flapper, and the other leg of the spring is held by a "stop post". Thus, each spring undergoes less total angular deflection as the flappers move from the closed position to the open position. Stiffer springs may be used since less deflection occurs, with the result that greater torque can be exerted by the spring against the flapper for small angular deflections of the flapper about its nearly closed position.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The basic elements of this novel check valve are shown in FIGS. 1 and 2. A semicircular right flapper 2 and a semicircular left flapper 3 lie on the body 1 with their straight edges lying along center rib 4 of the body 1. The hinge pin 7 is inserted through the hinge pin holes 31 in the body 1, running through the upper body lug bearing 15, upper right hinge lug 11, upper plate lug bearing 16, upper left hinge lug 12, independent spring 21, independent spring 22, lower right hinge lug 13, lower plate lug bearing 17, lower left hinge lug 14, and lower body lug bearing 18. Two hinge pin retainers 41 inserted into hinge pin holes 31 hold the hinge pin 7 in place. The stop pin 6 is inserted through stop pin holes 32 in the body 1, running through the hooked leg 24 of spring 21 and the hooked leg 25 of spring 22. Two stop pin retainers 42 inserted into stop pin holes 32 hold the stop pin 6 in place.
Ordinarily, the installed check valve is oriented with the rib 4 in a vertical position.
While the specific embodiment shown only uses one spring for each flapper, it is expressly understood that more than one spring may be used for each flapper. Moreover, while only helical torsion springs are shown, it is expressly understood that any torsion spring or torque producing means may be substituted. Since this novel design permits the use of shorter, stiffer (higher torque) springs, the ability to use multiple springs is enhanced.
As is shown in the comparison of FIGS. 3 and 4, the total angular deflection of the independent spring used in this novel design is considerably less than that of a non-independent spring. Referring to FIG. 4, the conventional spring is "preloaded" such that usually it is bent approximately 180° (90° for each end) from its unstressed position when the flappers are closed. This biases the flappers toward the closed position even when nearly closed or even seated. When both flappers are fully open, the spring has been deflected approximately an additional 170°, for a total angular deflection of approximately 350° (175° for each end of the spring).
In this new design, the springs may each be preloaded about 50° to 80° or less from their unstressed positions, as is shown in FIG. 3. This reduced angular preloading of each spring is made possible because: (1) each spring acts upon only one flapper, and need be preloaded less than a single spring acting on both flappers; and (2) the use of stiffer springs reduces the required angular deflection for a specific amount of torque to be preloaded. When a flapper is in its fully open position, its spring is deflected approximately an additional 85°, for a total angular deflection of about 135° to 165°, as compared with the 350° angular deflection of the spring in a conventional design.
A further advantage of the novel independent spring design is that the characteristics of each spring may be tailored to compensate for any non-uniform or assymetrical response of the flappers. As discussed earlier, the two flappers may require different amounts of force to close because of inequalities in frictional forces or other forces acting upon them. Quite typically, one of the flappers will be more difficult to close because of additional frictional resistance acting upon it. In a conventionally designed check valve, this results in the other flapper closing first, and the practically exhausted spring then acting upon only the nearly closed flapper. This hesitation in complete valve closure can result in allowing the flow through the check valve to reverse before the slower flapper has seated, thereby causing the flapper to slam shut with a resulting pressure surge. However, when independent springs are used, a higher torque spring may be used to act upon the flapper having more frictional resistance, thereby providing that flapper with additional closing force and higher torque acting upon it when nearly closed. By proper design of the relative strengths of the springs, the valve can be made wherein the flappers close synchoronously, or one flapper closes slightly before the other.
Also, since each independent spring undergoes less total angular deflection, the springs may typically be shorter than those of the conventional design, thereby allowing more springs to be used. The use of multiple independent springs for each flapper may be desirable, for in a valve of such design one or more springs would continue to provide biasing torque to the flapper should one of the springs acting on that flapper fail.
The use of stiffer or higher torque springs acting on the flappers increases the angular acceleration of the flapper toward the seat. The greater the angular acceleration, the faster the valve response. If the movement of the flapper plates matches the deceleration of the fluid flow through the check valve, pressure surges and "hammer" can be minimized. However, if insufficient torque acts on the flapper plate, the valve will still be partially opened when the rate of flow has gone to zero and the direction of flow starts to reverse. Some backflow will then occur, resulting in a pressure surge and hammer when the valve finally closes. Since stiffer springs may be used in this novel design because of the reduced total angular deflection of the spring between the open and closed positions, more torque can be exerted by the spring against the flapper plate. The increased torque acting upon each flapper enables the flapper to close more quickly and will improve valve performance.
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An improvement in multi-flapper check valves wherein each flapper is urged toward closure by an independent spring or springs, thereby improving the valve response for closure.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a liquid crystal display device provided with a pixel electrode having in one pixel a reflective electrode reflecting outside light and a transmissive electrode transmitting light from a back light source, and a manufacturing method thereof.
2. Related Background Art
In a general liquid crystal display device, a thin film of liquid crystal is placed between two substrates. Each of the substrates has an electrode on the surface facing the liquid crystal film. The polarizers are placed on both sides of the substrates. In a transmissive liquid crystal display device, a backlight is positioned behind the substrates. Alignment treatment is provided on the substrate surfaces having the electrode. A liquid crystal having desirable director, the average direction of liquid crystal molecules, exhibits birefringence. Incident light coming from the backlight through the polarizer becomes elliptic polarized light due to the birefringence, and enters the polarizer on the opposite side. When applying voltage between the upper and lower electrodes, it rearranges the director to change the birefringence of the liquid crystal film, thereby changing the condition of the elliptic polarized light entering the polarizer on the opposite side. Electro-optical effect of changing intensity and spectrum of light passing through the liquid crystal display device is thus obtained.
There are two types of liquid crystal display devices: a transmissive liquid crystal display device displaying images with a backlight (rear light source) mounted at the back or side thereof, and a reflective liquid crystal display device displaying images by reflecting incoming ambient light on a reflector mounted to a substrate. The transmissive liquid crystal display device has the problem that displayed images are invisible under bright ambient light because display light is darker than the ambient light. On the other hand, the reflective liquid crystal display device has the problem of having significantly decreased visibility under dark ambient light.
In order to solve the above problems, a liquid crystal display device employing a semi-transmissive reflective film transmitting a portion of light while reflecting another portion of light, which will be referred to hereinafter as a semi-transmissive liquid crystal display device, has been proposed. The semi-transmissive liquid crystal display device is disclosed in Japanese Patent Application Laid-Open No. H07-333598, No. 2000-19563, and No. 2000-305110, for example.
SUMMARY OF THE INVENTION
However, the conventional semi-transmissive liquid crystal display devices disclosed in the above applications have problems of complicated manufacturing processes and low manufacturing yields.
The present invention has been accomplished to solve the above problems and an object of the present invention is thus to provide a liquid crystal display device manufactured in simple processes while having high manufacturing yields, and a method of manufacturing the same.
A liquid crystal display device according to the present invention is a liquid crystal display device provided with liquid crystal material sealed between substrates and having a pixel electrode in a pixel on one of the substrates, the pixel electrode having a reflective electrode (for example, third metal thin films 10 and 11 in the following preferred embodiment of the invention) for reflecting light from outside, a transmissive electrode (for example, a conductive thin film 9 in the preferred embodiment of the invention) for transmitting light from a back light source, wherein the reflective electrode and the transmissive electrode are laminated with no insulating layers interposed therebetween. The liquid crystal display devices having the above configuration is easy to manufacture and produces high manufacturing yields.
The reflective electrode is preferably formed at a top layer directly under an alignment layer. It is also preferable to configure the reflective electrode by forming a conductive material to cover the reflective electrode before pattern formation, and removing the conductive material after the pattern formation, in order to prevent erosion of the transmissive electrode.
In a preferred embodiment, material of the reflective electrode includes aluminum, and material of the conductive material includes one of chromium, molybdenum, tantalum, and tungsten.
It is also preferable that a part of the transmissive electrode is removed at a connection between the transmissive electrode and the first metal thin film, and/or at a connection between the transmissive electrode and the second metal thin film, and the part is covered with the reflective electrode, so that the reflective electrode is connected to the first metal thin film and/or the second metal thin film. The configuration reduces connection resistance between the transmissive electrode and the first or second metal thin film.
Further, a periphery of the transmissive electrode in a pixel is preferably covered with the reflective electrode for stronger adhesion.
It is also preferable that the transmissive electrode has a concavity in a pixel and inner side portion of the concavity is covered with the reflective electrode.
More preferably, the overlap of the reflective electrode with the inner side portion of the concavity on the transmissive electrode in the pixel is 2 μm to 6 μm.
Besides, it is preferable in the pixel that a semiconductor film of a thin film transistor (TFT) section extends to a lower part of a source line.
On the other hand, a manufacturing method of a liquid crystal display device according to the present invention is a manufacturing method of a liquid crystal display device provided with liquid crystal material sealed between substrates and having a pixel electrode in a pixel on one of the substrates, the pixel electrode having a reflective electrode for reflecting light from outside and a transmissive electrode for transmitting light from a back light source, the manufacturing method having a step of forming the transmissive electrode and a step of forming the reflective electrode on the transmissive electrode, with no insulating layers interposed therebetween. In this method, the liquid crystal display is easy to manufacture and produces high manufacturing yields.
It is preferable that the step of forming the reflective electrode includes a step of forming a conductive material to cover the reflective electrode before pattern formation, and a step of removing the conductive material after the pattern formation
In a preferred embodiment, material of the reflective electrode includes aluminum, and material of the conductive material includes one of chromium, molybdenum, tantalum, and tungsten.
Another manufacturing method of a liquid crystal display device according to the present invention is a manufacturing method of a liquid crystal display device provided with liquid crystal material sealed between substrates and having a pixel electrode in a pixel on one of the substrates, the pixel electrode having a reflective electrode for reflecting light from outside and a transmissive electrode for transmitting light from a back light source, the manufacturing method having a step of forming and patterning the first metal thin film on an insulating substrate; a step of depositing the first insulation layer, a semiconductor active layer, an ohmic contact layer, and the second metal thin film; a step of forming a resist pattern by halftone exposure; and a step of patterning the semiconductor active layer, the ohmic contact layer, and the second metal thin film by etching. In this method, it is possible to decrease photographic processes to facilitate manufacture and attain high manufacturing yields.
It is preferable that the above method further has, after the step of patterning the semiconductor active layer, the ohmic contact layer, and the second metal thin film by etching, a step of forming the second insulation layer; a step of forming a uneven pattern by halftone exposure; and a step of patterning the first and second insulation layer by etching. In this method, it is possible to further decrease photographic processes to facilitate manufacture and attain high manufacturing yields.
Another manufacturing method of a liquid crystal display device according to the present invention is a manufacturing method of a liquid crystal display device provided with liquid crystal material sealed between substrates and having a pixel electrode in a pixel on one of the substrates, the pixel electrode having a reflective electrode for reflecting light from outside and a transmissive electrode for transmitting light from a back light source, the manufacturing method having a step of forming and patterning the first metal thin film on an insulating substrate; a step of depositing the first insulation layer, a semiconductor active layer, an ohmic contact layer, and the second metal thin film; a step of depositing the semiconductor active layer, the ohmic contact layer, and the second metal thin film; a step of forming a resist pattern by halftone exposure; and, after the step of patterning the semiconductor active layer, the ohmic contact layer, and the second metal thin film by etching, having a step of forming the second insulation layer; a step of forming a uneven pattern by halftone exposure; and a step of patterning the first and second insulation layers by etching. In this manufacturing method, it is possible to decrease photographic processes to facilitate manufacture and attain high manufacturing yields.
It is possible that the step of forming the transmissive electrode includes a step of forming amorphous indium tin oxide (ITO); a step of patterning the amorphous ITO; and a step of crystallizing the amorphous ITO. It is preferable in the step of crystallizing the amorphous ITO that the amorphous ITO is heated to 200° C. or above for crystallization.
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not to be considered as limiting the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1 G are views to show a process flow chart of a liquid crystal display device according to the first embodiment of the present invention.
FIGS. 2A to 2 F are views to show a process flow chart of a liquid crystal display device according to the second embodiment of the present invention.
FIGS. 3A to 3 F are views to show a process flow chart of a liquid crystal display device according to the third embodiment of the present invention.
FIGS. 4A to 4 E are views to show a process flow chart of a liquid crystal display device according to the fourth embodiment of the present invention.
FIG. 5 is a principle view to show a case of forming an uneven pattern by deposition of an organic layer, exposure, and development.
FIG. 6 is a view to show a configuration example of a halftone mask used in the present invention.
FIGS. 7A to 7 G are views to show a process flow chart of a liquid crystal display device according to another embodiment.
FIG. 8 is a view to show a process flow chart of a liquid crystal display device according to the fifth embodiment of the present invention.
FIG. 9 is a view to show a process flow chart of a liquid crystal display device according to the sixth embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1A to 1 G show a manufacturing process flow chart of a semi-transmissive liquid crystal display device according to the first embodiment of the present invention. In the manufacturing process, a semi-transmissive TFT array is produced in seven times of photolithography processes.
First, a glass substrate to be used as an insulating substrate is cleaned. A transparent insulating substrate such as a glass substrate is used as the insulating substrate. While the insulating substrate can have any thickness, the substrate not over 1.1 mm thick is preferable for a thin liquid crystal display device. If the insulating substrate is too thin, however, it could be distorted by thermal history of film depositions and other processes, causing decreased patterning accuracy. Therefore, the thickness of the insulating substrate should be decided in consideration of the processes to be used. Besides, in a case that the insulating substrate is composed of brittle fracturable material such as glass, it is preferable to cut off the edges of the substrate in order to prevent any foreign matter from getting inside due to chipping. It is also preferable to make a notch on the insulating substrate to identify its direction, so that a direction of substrate processing can be easily determined in the following processes.
In the next place, the first metal thin film 1 is formed by a deposition process such as sputtering. The first metal thin film 1 is a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example. Chromium having 200 nm film thickness is used in a preferred embodiment. As the first metal thin film 1 , it is preferable to use a metal thin film being resistant to surface oxidation, or being conductive though oxidized, and at least its surface is preferably one of chromium, titanium, tantalum, and molybdenum, because a contact hole will be formed on the first metal thin film 1 by dry etching and also a conductive thin film will be deposited thereon in the following processes. Besides, the first metal thin film 1 may be a laminate of different kinds of metal thin films, or a metal thin film having different composition along the film thickness. In a case that material including aluminum is used as the first metal thin film, aluminum nitride having surface resistivity of 10 to 1000μΩ is desirable.
Then, the first metal thin film is patterned with a gate electrode, a gate line, a storage capacitor electrode, and a storage capacitor line by the first photolithography process. A configuration shown in FIG. 1A is thereby formed. The photolithography process consists of the following steps: (1) After cleaned, the TFT array substrate is coated with a photoresist and then dried. (2) The photoresist is exposed to light through a mask pattern on which a prescribed pattern has been formed, and then developed. The photoresist onto which a mask pattern is projected is thereby photolithographically formed on the TFT array substrate. (3) After heat-hardened, the photoresist is etched away from the substrate. If the photoresist and the TFT array substrate have such a low fluidity as to repel the photoresist, conduct a treatment such as ultraviolet (UV) cleaning before the photoresist coating, and vapor-coating of hexamethyldisilazane (HMDS) for the better fluidity. If there is adhesion failure of the photoresist to the TFT array substrate, causing to strip the photoresist away, increase heat-hardening temperature, or prolong heat-hardening time. The etching of the first metal thin film can be wet etching using a known etchant (for example, a solution of a mixture of cerium ammonium nitrate and nitric acid if the first metal thin film composed of chromium). The first metal thin film 1 is preferably etched so that a pattern edge has a tapered shape in order to prevent short-circuit caused by height difference from another line. The pattern edge is therefore etched to have a trapezoid shape of the gate line. In addition to the gate electrode, gate line, storage capacitor electrode, and storage capacitor line, there are also formed in this process marks and lines necessary for the TFT array substrate formation.
In the third place, the first insulation layer 2 , a semiconductor active layer 3 , and an ohmic contact layer 4 are deposited in succession by a plasma chemical vapor deposition (CVD) process. As the first insulation layer 2 to be a gate insulation layer, a SiNx film, SiOy film, SiOzNw film, or a lamination film of those is used (x, y, z, and w are all positive numbers). The first insulation layer 2 is approximately 300 nm to 600 nm thick. The first insulation layer 2 is preferably thicker than the first metal thin film 1 because the thinner film thickness causes short-circuit at a crossing point between the gate line and the source line. In terms of display properties, on the other hand, the thinner film thickness is preferable because a thick film causes reduced on-state current of the TFT. In a preferred embodiment, the first insulation layer 2 is formed by depositing SiN film 300 nm thick and further depositing SiN film 100 nm thick.
As the semiconductor active layer 3 , an amorphous silicon (a-Si) film or a poly silicon (p-Si) film is used. The semiconductor active layer 3 is approximately 100 nm to 300 nm thick. If the film is too thin, it causes dissolution of the ohmic contact layer 4 in a dry etching process which will be detailed later; on the other hand, if the film is too thick, it causes reduction of on-state current of the TFT. Therefore, the film thickness is determined by controllability of etching depth at the time of dry-etching of the ohmic contact layer 4 , and a necessary amount of on-state current of the TFT. In a case of using an a-Si film as the semiconductor active layer 3 , an interface of the first insulation layer 2 and the a-Si film is preferably a SiNx film or a SiOzNw film for better controllability of Vth of the TFT, that is, gate voltage to make the TFT in a conduction state, and for reliability. On the other hand, if using a p-Si film as the semiconductor active layer 3 , an interface of the first insulation layer 2 and the p-Si film is preferably a SiOy film or a SiOzNw film for better controllability of Vth of the TFT and for reliability. Besides, in the case of using the a-Si film as the semiconductor active layer 3 , it is desirable to deposit a film with a smaller deposition rate in a lower part adjacent to the interface with the first insulation layer 2 , and with a larger deposition rate in an upper layer, in order to obtain the TFT property of larger mobility in shorter deposition time, and reduce leakage current during the off-state of the TFT. In a preferred embodiment, an i-a-Si film 150 nm thick is deposited as the semiconductor active layer 3 .
As the ohmic contact layer 4 , a n-a-Si film or a n-p-Si film that is a film a-Si doped with phosphorus (P) is used. The ohmic contact layer 4 is approximately 20 nm to 70 nm thick. The SiNx film, SiOy film, SiOzNw film, a-Si film, p-Si film, n-a-Si film, and n-p-Si film can be deposited by using known gas such as SiH 4 , NH 3 , H 2 , NO 2 , PH 3 , N 2 , and mixed gas of those. In a preferred embodiment, a n-a-Si film 30 nm thick is deposited as the ohmic contact layer 4 .
Then, the semiconductor active layer 3 and the ohmic contact layer 4 are patterned on at least a section where the TFT is to be formed, by the second photolithography process. A configuration shown in FIG. 1B is thereby formed. The first insulating layer 2 remains all over the substrate. It is preferable that the semiconductor active layer 3 and the ohmic contact layer 4 remain by patterning in a grade crossing point between the source line, and the gate line and the storage capacitor line, in addition to the section where the TFT will be formed, for larger resistance voltage at the crossing point. Besides, the semiconductor active layer 3 and the ohmic contact layer 4 in the TFT section preferably extend to a lower part of the source line so that the source electrode does not cross the edge of the semiconductor active layer 3 and the ohmic contact layer 4 where there is a difference in level, to avoid disconnection of the source electrode.
The semiconductor active layer 3 and the ohmic contact layer 4 can be dry-etched using known gas composition such as mixed gas of SF 6 and O 2 or of CF 4 and O 2 .
In the fourth place, the second metal thin film is formed by a deposition process such as sputtering. As the second metal thin film, chromium, molybdenum, tantalum, titanium, aluminum, copper, alloy combining another substance with one of those elements, or lamination film of those is used for example. Chromium of 200 nm thick is deposited in a preferred embodiment.
Then, the second metal thin film is patterned with the source electrode 5 and the drain electrode 6 by the third photolithography process. A configuration shown in FIG. 1C is thereby formed. The source electrode 5 is formed ranging over the crossing point between the source line and the gate line. The drain electrode 6 is formed ranging over a reflecting section. Next, the ohmic contact layer 4 is etched to remove a central part thereof in the TFT section, and expose the semiconductor active layer 3 . The ohmic contact layer 4 can be dry-etched using known gas composition such as mixed gas of SF 6 and O 2 or of CF 4 and O 2 .
In the fifth place, the second insulation layer 7 is formed by the plasma CVD process. An organic layer 8 is then formed by a process such as spin coating, slit coating, and transcription. SiN 100 nm thick is used as the second insulation layer 7 in a preferred embodiment. The organic layer 8 is a known photosensitive organic layer such as PC 335 or PC 405 made by JSR Corporation.
Then, the organic layer 8 is patterned with a form shown in FIG. 1D by the fourth photolithography process. More specifically, the organic layer 8 is patterned so that the first insulation layer 2 is exposed in the section where the first insulation layer 2 and the second insulation layer 7 are to be removed by the following fifth photolithography process. The organic layer 8 is also partly removed in the reflecting section so that the section has an uneven surface.
Then, the organic layer is patterned by the fifth photolithography process. The organic layer in the section where the first and second insulation layers 2 and 7 are to be removed is removed here. The organic layer in the section having an uneven surface is not removed, and proper diffusion property can be obtained by moderately reducing unevenness of the first layer. Subsequently, taper etching is performed to form a configuration shown in FIG. 1 E. In the gate terminal, the first insulation layer 2 and the second insulation layer 7 are both removed, and the first metal thin film 1 is exposed, to form a contact hole electrically connecting the gate line with a driving signal source. In the source terminal, the second insulation layer 7 is removed, and the second metal thin film is exposed. In an area between the TFT section and the reflecting section, the second insulation layer is removed, and the drain electrode 6 is exposed. Further, in the transmitting section, the first insulation layer and the second insulation layer are both removed, and the first insulating substrate is exposed. In a case of not removing the organic layer in the transmitting section, it is preferable to add a known bleaching process, that is, a process to enhance transparency of the photosensitive organic layer by ultraviolet light exposure, after the patterning of the organic layer by the photolithography process.
In the sixth place, the conductive thin film 9 is formed by a deposition process such as sputtering. As the conductive thin film 9 , ITO or SnO 2 , which is a transparent conductive film, can be used, and the ITO is especially preferable for better chemical stability. 80 nm thick ITO is used as the conductive thin film 9 in a preferred embodiment. While the ITO may be either crystallized ITO or amorphous ITO, it is necessary for the amorphous ITO to be heated to 180° C. and above for crystallization before depositing the third metal thin film. The amorphous ITO is heated to 200° C. or above in a preferred embodiment.
Then, the conductive thin film 9 is patterned with a pixel electrode and so on, as shown in FIG. 1F, by the sixth photolithography process. Depending on the material used, the conductive thin film 9 may be wet etched using known etchant (for example, a solution of a mixture of hydrochloric acid and nitric acid if crystallized ITO is used). If ITO is used as the conductive thin film 9 , dry-etching using known gas composition such as HI and HBr is also possible. In addition to the pixel electrode, there are also formed in this process an electrode of the conductive thin film 9 in a transfer terminal for electrically connecting an opposed substrate and the TFT array substrate using resin including conductive particles. The amorphous ITO can be patterned in the same way as the crystallized ITO if after the heating, while it is patterned using a solution of a mixture of known oxalic acid if before the heating.
In the seventh place, the third metal thin films 10 and 11 are formed by a deposition process such as sputtering. As the third metal thin films 10 and 11 , a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example, is used. The metal thin film 10 prevents the metal thin film 11 from being broken at a portion where there is a difference in level, such as a contact hole. If the breakage is negligible, it is possible not to form the metal thin film 10 , which eliminates one step and reduces costs. In a preferred embodiment, after chromium 100 nm thick is deposited, alloy of aluminum and Cu 300 nm thick is deposited, and chromium 100 nm thick is further deposited thereon. Chromium is provided at a top layer directly under an alignment layer because, if the alloy of aluminum and Cu is exposed, it causes a corrosion of the ITO 9 at the time of development in the following photolithography process. Instead of Chromium; molybdenum, tantalum, or tungsten may be used for the same effect.
Then, the third metal thin films 10 and 11 , and the chromium of the top layer are patterned with a form of a reflective electrode, and then the chromium of the top layer is etched away, to form the reflective electrode, by the seventh photolithography process. Here, the removal of the organic layer in the transmitting section forms a concavity and could cause alignment defect of liquid crystals due to a difference in level on the organic layer, which decreases display quality. To prevent this problem, an inner side portion of the concavity is preferably covered with the reflective electrode as shown in FIG. 1 G. Various studies show that the alignment defect can occur in a range between 2 μm and 6 μm away from the inner side portion. Therefore, the reflective electrode need to have an overlap of 2 μm at least, and 6 μm is enough even in a case where smaller aperture ratio of transmission is allowable, which means 2 μm to 6 μm is a preferable length. If layers are deposited in the order of chromium, aluminum (the metal thin film 11 ), and chromium (the metal thin film 10 ) from the top layer, the chromium of the top layer and the chromium of the third layer (the metal thin film 10 ) can be etched at the same time. In this case, a reflector can be formed in the order of resist patterning, chromium etching, aluminum etching, chromium etching, resist striping, and chromium etching, or in the order of resist patterning, chromium etching, aluminum etching, resist striping, and chromium etching. Also, if the metal thin film 10 and a metal thin film of the top layer are composed of the same material, they can be removed in one etching process. The reflective electrode is formed as a lamination layer of the metal thin film 10 composed of chromium, and the metal thin film 11 composed of alloy of aluminum and Cu on top thereof. The chromium of the top layer has been provided for preventing corrosion of the ITO 9 , and it is removed in this step for improved reflectance. The third metal thin film can be wet-etched using known etchant. A configuration shown in FIG. 1G is thereby formed. As described above, in a liquid crystal display device according to the present embodiment of the invention, the reflective electrodes 10 and 11 , and the conductive thin film 9 are formed without having an insulation layer in between.
As explained in the foregoing, the TFT array substrate is formed by seven steps of the photolithography process, attaining high manufacturing yields.
Though the first embodiment explains a case where two layers of the third metal thin films, 10 and 11 are formed, the present invention is not restricted thereto, whereas it can be a single layer of the third metal thin film 11 .
The second, third, and fourth embodiments of the present embodiment will explain a case where a single layer of the third metal thin film 11 is formed.
Use of a developer that prevents ITO from corrosion, such as ELM-DSA made by Mitsubishi Chemical Corporation in the photolithography process to form the metal thin films 10 and 11 can eliminate the metal of the top layer, that is, the metal composed of one of molybdenum, tantalum, and tungsten, to reduce the number of manufacturing steps. The following embodiments will explain a case where chromium is provided at the top layer.
FIGS. 2A to 2 F show a process flow chart of a semi-transmissive liquid crystal display device according to the second embodiment of the present invention. In this process, a semi-transmissive TFT array is produced in six times of photolithography processes.
First, a glass substrate 0.7 mm thick to be used as an insulating substrate is cleaned. The insulating substrate is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the next place, the first metal thin film 1 is formed by a deposition process such as sputtering. The first metal thin film 1 is a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example. A chromium film 200 nm thick is used in a preferred embodiment. The metal thin film 1 is the same as the one explained in the above first embodiment, and the explanation is omitted here.
Then, the first metal thin film is patterned with a gate electrode, a gate line, a storage capacitor electrode, and a storage capacitor line by the first photolithography process. A configuration shown in FIG. 2A is thereby formed. The manufacturing method of this configuration is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the third place, the first insulation layer 2 , a semiconductor active layer 3 , an ohmic contact layer 4 , and the second metal thin film are deposited in succession. In a preferred embodiment, a lamination film of a SiN film 300 nm thick and a SiN film 100 nm thick is used as the first insulation layer 2 to be a gate insulation layer. An i-a-Si film 150 nm thick is used as the semiconductor active layer 3 . A n-a-Si film 30 nm thick is used as the ohmic contact layer 4 . A chromium film 200 nm thick is used as the second metal thin film. The SiN film, a-Si film, and n-a-Si film are deposited by a plasma CVD apparatus. When depositing the ohmic contact layer 4 , a film is doped with PH 3 to form the n-a-Si film. Chromium is deposited by a DC magnetron sputtering apparatus, for example.
Then, a resist pattern to form a source line, a metal pad at a source terminal, a drain electrode, a semiconductor active layer 3 , and so on is formed by the second photolithography process. Halftone exposure is applied in the second photolithography process.
The halftone exposure will be explained hereinafter with reference to FIG. 5 and FIG. 6. A mask as shown in FIG. 5 is used in the halftone exposure. A spatial frequency of an exposure pattern on the mask is higher than pattern resolution of an exposure apparatus (1.6 μm, for example) so that the mask pattern is not resolved on a photoresist, thereby adjusting exposure intensity. The photoresist is illuminated through the mask, and adjustment of an amount of the illumination light allows control of remaining film thickness of the photoresist. Therefore, as shown in FIG. 6, adjustment of the amount of light within the range in which the photoresist is dissolved by development changes the remaining film thickness of the photoresist accordingly. More specifically, smaller amount of the photoresist remains in the area receiving a large amount of light, while larger amount of the photoresist remains in the area receiving a smaller amount of light.
Novolac resin-based positive resist is used in the case here, and the resist is coated by 1.5 μm by a spin coater. The resist coating is followed by pre-bake for 90 seconds at 120° C. Then, the resist pattern is formed by 1000 msec exposure using a halftone mask pattern. The mask pattern is a regular mask pattern of chromium, having a striped shape to form the resist pattern of line/space=1.5 μm/1.5 μm. The exposure apparatus used here is a regular stepper or a mirror projection-type, and a light source is g-line and h-line of a high-pressure mercury lamp. Since the striped pattern is smaller than a resolution limit of the exposure apparatus, the resist is not exposed to have the striped pattern, and the exposure amount there becomes smaller than in other exposed area, on average.
Then, the pattern is developed by an organic alkali developer, and post-bake for 180 seconds at 100° C. to 120° C. comes next to volatilize solvent in the resist and also to strengthen adhesion of the resist to the chromium. Further, oven-bake at 120° C. to 130° C. follows for the stronger adhesion between the resist and the chromium. The bake temperature should not be too high here to prevent the resist edge from flagging. After that, the chromium film is etched using a ((NH 4 )2[Ce (NO 3 ) 6 ]+HNO 3 +H 2 O) solution. Then, the ohmic contact layer 4 and the semiconductor active layer 3 are etched using (HCl+SF 6 ) gas. Resist ashing by oxygen plasma is then performed for 60 seconds at a pressure of 40 Pa so as to expose the chromium film in the resist pattern. In the ashing process, control of a resist opening width is easier in a reactive ion etching (RIE) mode than in a plasma etching (PE) mode. The configuration shown in FIG. 2B is thereby formed.
Then, after oven-bake at 130° C. to 140° C., the chromium film is etched using a ((NH 4 )2[Ce (NO 3 ) 6 ]+HNO 3 +H 2 O) solution. The ohmic contact layer is removed after that.
In the fourth place, the second insulation layer 7 is formed by the plasma CVD process.
Then, the organic layer 8 is patterned with a form shown in FIG. 2C by the third photolithography process. More specifically, the organic layer 8 is patterned so that the first insulation layer 2 is exposed in the section where the first insulation layer 2 and the second insulation layer 7 are to be removed by the following fourth photolithography process. The organic layer 8 is also partly removed in the reflecting section so that the section has an uneven surface.
In the fifth place, the organic layer is patterned by the fourth photolithography process. The organic layer in the section where the first and second insulation layer 2 and 7 are to be removed is removed here. The organic layer in the section having an uneven surface is not removed, and proper diffusion property can be obtained by moderately reducing unevenness in the first layer. Subsequently, taper etching is performed to form a configuration shown in FIG. 2 D. In the gate terminal, the first insulation layer 2 and the second insulation layer 7 are both removed, and the first metal thin film 1 is exposed, to form a contact hole electrically connecting the gate line with a driving signal source. In the source terminal, the second insulation layer 7 is removed, and the second metal thin film is exposed. In an area between the TFT section and the reflecting section, the second insulation layer is removed, and the drain electrode 6 is exposed. Further, in the transmitting section, the first insulation layer and the second insulation layer are both removed, and the first insulating substrate is exposed.
In the sixth place, the conductive thin film 9 is formed by a deposition process such as sputtering. ITO 80 nm thick is used as the conductive thin film 9 in a preferred embodiment. While the ITO may be either crystallized ITO or amorphous ITO, it is necessary for the amorphous ITO to be heated to 180° C. and above for crystallization before depositing the third metal thin film. The amorphous ITO is heated to 200° C. or above in a preferred embodiment.
Then, the conductive thin film 9 is patterned with a pixel electrode and so on, as shown in FIG. 2E, by the fifth photolithography process. Depending on the material used, the conductive thin film 9 may be wet-etched using known etchant (for example, a solution of a mixture of hydrochloric acid and nitric acid if crystallized ITO is used). If ITO is used as the conductive thin film 9 , dry-etching using known gas composition such as HI and HBr is also possible. In addition to the pixel electrode, there are also formed in this process an electrode of the conductive thin film 9 in a transfer terminal for electrically connecting an opposed substrate and the TFT array substrate using resin including conductive particles. The amorphous ITO can be patterned in the same way as the crystallized ITO if after the heating, while it is patterned using a solution of a mixture of known oxalic acid if before the heating.
In the seventh place, the third metal thin film 11 is formed by a deposition process such as sputtering. As the third metal thin film 11 , a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example, is used. In a preferred embodiment, alloy of aluminum and Cu 300 nm thick is deposited, and chromium 100 nm thick is further deposited thereon. Chromium is provided at a top layer directly under an alignment layer because, if the alloy of aluminum and Cu is exposed, it causes a corrosion of the ITO 9 at the time of development in the following photolithography process. Instead of Chromium; molybdenum, tantalum, or tungsten may be used for the same effect.
Then, the third metal thin film 11 and the chromium of the top layer are patterned with a form of a reflective electrode, and then the chromium of the top layer is etched away, to form the reflective electrode, by the sixth photolithography process. If the metal thin film 11 is chromium, it can be etched at the same time as the chromium of the top layer. The chromium of the top layer has been provided for preventing corrosion of the ITO 9 , and it is removed in this step for improved reflectance. The third metal thin film can be wet-etched using known etchant. A configuration shown in FIG. 2F is thereby formed. As described above, in a liquid crystal display device according to the present embodiment of the invention, the reflective electrode 11 and the conductive thin film 9 are formed without having a insulation layer in between.
As explained in the foregoing, the TFT array substrate is formed by six steps of the photolithography process, attaining high manufacturing yields.
FIGS. 3A to 3 F show a process flow chart of a semi-transmissive liquid crystal display device according to the third embodiment of the present invention. In this process, a semi-transmissive TFT array is produced using six masks.
First, a glass substrate 0.7 mm thick to be used as an insulating substrate is cleaned. The insulating substrate is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the next place, the first metal thin film 1 is formed by a deposition process such as sputtering. The first metal thin film 1 is a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example. A chromium film 200 nm thick is used in a preferred embodiment. The metal thin film 1 is the same as the one explained in the above first embodiment, and the explanation is omitted here.
Then, the first metal thin film is patterned with a gate electrode, a gate line, a storage capacitor electrode, and a storage capacitor line by the first photolithography process. A configuration shown in FIG. 3A is thereby formed. The manufacturing method of this configuration is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the third place, the first insulation layer 2 , a semiconductor active layer 3 , and an ohmic contact layer 4 are deposited in succession by a plasma chemical vapor deposition (CVD) process. Then, a configuration shown in FIG. 3B is formed by etching and so on. The manufacturing method of this configuration is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the fourth place, the second metal thin film is formed by a deposition process such as sputtering. Chromium, for example, is used as the second metal thin film 1 . A chromium film 200 nm thick is deposited in a preferred embodiment.
Then, the second metal thin film is patterned with the source electrode 5 and the drain electrode 6 by the third photolithography process. A configuration shown in FIG. 3 C is thereby formed. The source electrode 5 is formed ranging over the crossing point between the source line and the gate line. The drain electrode 6 is formed ranging over a reflecting section. In this process, a central part of the ohmic contact layer 4 in the TFT section is removed to expose the semiconductor active layer 3 . The ohmic contact layer 4 can be dry-etched using known gas composition such as mixed gas of SF 6 and O 2 or of CF 4 and O 2 .
In the fifth place, the second insulation layer 7 is formed by the plasma CVD process. An organic layer 8 then is formed by a process such as spin coating, slit coating, and transcription. SiN 100 nm thick is used as the second insulation layer 7 in a preferred embodiment. The organic layer 8 is a known photosensitive organic layer such as PC 335 or PC 405 made by JSR Corporation.
Then, the organic layer 8 is patterned with a form shown in FIG. 3D by the fourth photolithography process. Halftone exposure is applied in the fourth photolithography process. The halftone exposure is the process explained in the second embodiment of the invention. By the halftone exposure and the following etching, in the gate terminal, the organic layer at the contact hole electrically connecting the gate line with a driving signal source is removed. The first insulation layer 2 and the second insulation layer 7 are both removed by the etching. The first metal thin film 1 is therefore exposed. In the source terminal, the second insulation layer 7 is removed, and the second metal thin film is exposed. In an area between the TFT section and the reflecting section, the second insulation layer is removed, and the drain electrode 6 is exposed. Further, in the transmitting section, the first insulation layer and the second insulation layer are both removed, and the first insulating substrate is exposed. Since the organic layer remains in a concave part of the uneven surface section in the reflective section, and the second insulation layer is not removed, the organic layer forms an uneven surface.
In the sixth place, the conductive thin film 9 is formed by a deposition process such as sputtering. In a transmissive liquid crystal display device, ITO or SnO 2 , a transparent conductive film, can be used as the conductive thin film 9 , and the ITO is especially preferable for better chemical stability. ITO 80 nm thick is used as the conductive thin film 9 in a preferred embodiment. While the ITO may be either crystallized ITO or amorphous ITO, it is necessary for the amorphous ITO to be heated to 180° C. and above for crystallization before depositing the third metal thin film. The amorphous ITO is heated to 200° C. or above in a preferred embodiment.
Then, the conductive thin film 9 is patterned with a pixel electrode and so on, as shown in FIG. 3E, by the fifth photolithography process. Depending on the material used, the conductive thin film 9 may be wet-etched using known etchant (for example, a solution of a mixture of hydrochloric acid and nitric acid if crystallized ITO is used). If ITO is used as the conductive thin film 9 , dry-etching using known gas composition such as HI and HBr is also possible. In addition to the pixel electrode, there are also formed in this process an electrode of the conductive thin film 9 in a transfer terminal for electrically connecting an opposed substrate and the TFT array substrate using resin including conductive particles. The amorphous ITO can be patterned in the same way as the crystallized ITO if after the heating, while it is patterned using a solution of a mixture of known oxalic acid if before the heating.
In the seventh place, the third metal thin film 11 is formed by a deposition process such as sputtering. As the third metal thin film 11 , a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example, is used. In a preferred embodiment, after chromium 100 nm thick is deposited, alloy of aluminum and Cu 300 nm thick is deposited, and chromium 100 nm thick is further deposited thereon. Chromium is provided at a top layer directly under an alignment layer because, if the alloy of aluminum and Cu is exposed, it causes corrosion of the ITO 9 at the time of development in the following photolithography process. Instead of Chromium; molybdenum, tantalum, or tungsten may be used for the same effect.
Then, the third metal thin film 11 and the chromium of the top layer are patterned with a form of a reflective electrode to form the reflective electrode, by the sixth photolithography process. If the metal thin film 11 is chromium, it can be etched at the same time as the chromium of the top layer. The third metal thin film can be wet-etched using known etchant. A configuration shown in FIG. 3F is thereby formed. As described above, in a liquid crystal display device according to the present embodiment of the invention, the reflective electrodes 11 and the conductive thin film 9 are formed without having a insulation layer in between.
As explained in the foregoing, the TFT array substrate is formed by six steps of the photolithography process, attaining high manufacturing yields.
FIGS. 4A to 4 E show a process flow chart of a semi-transmissive liquid crystal display device according to the fourth embodiment of the present invention. In this process, a semi-transmissive TFT array is produced in five times of photolithography processes.
First, a glass substrate 0.7 mm thick to be used as an insulating substrate is cleaned. The insulating substrate is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the next place, the first metal thin film 1 is formed by a deposition process such as sputtering. The first metal thin film 1 is a thin film 100 nm to 500 nm thick composed of one of chromium, molybdenum, tantalum, titanium, aluminum, copper, and alloy combining another substance with one of those elements, for example. A chromium film 200 nm thick is used in a preferred embodiment. The metal thin film 1 is the same as the one explained in the above first embodiment, and the explanation is omitted here.
Then, the first metal thin film is patterned with a gate electrode, a gate line, a storage capacitor electrode, and a storage capacitor line by the first photolithography process. A configuration shown in FIG. 4A is thereby formed. The manufacturing method of this configuration is the same as the one explained in the above first embodiment, and the explanation is omitted here.
In the third place, the first insulation layer 2 , a semiconductor active layer 3 , an ohmic contact layer 4 , and the second metal thin film are deposited in succession. In a preferred embodiment, a lamination film of a SiN film 300 nm thick and a SiN film 100 nm thick is used as the first insulation layer 2 to be a gate insulation layer. An i-a-Si film 150 nm thick is used as the semiconductor active layer 3 . A n-a-Si film 30 nm thick is used as the ohmic contact layer 4 . A chromium film 200 nm thick is used as the second metal thin film. The SiN film, a-Si film, and n-a-Si film are deposited by a plasma CVD apparatus. When depositing the ohmic contact layer 4 , a film is doped with PH 3 to form the n-a-Si film. Chromium is deposited by a DC magnetron sputtering apparatus, for example.
Then, a resist pattern to form a source line, a metal pad at a source terminal, a drain electrode, a semiconductor active layer 3 , and so on is formed by the second photolithography process. Halftone exposure is applied in the second photolithography process. The halftone exposure is the process explained in the second embodiment of the invention. This process is the same as the one explained in the second embodiment, and the explanation is omitted here. A configuration shown in FIG. 4B is thereby formed.
Then, after the oven-bake at 130° C. to 140° C., the chromium film is etched using a ((NH 4 )2[Ce(NO 3 ) 6 ]+HNO 3 +H 2 O) solution.
In the fourth place, the second insulation layer 7 and an organic layer 8 are formed by the plasma CVD process. A SiN film 100 nm thick is used as the second insulation layer 7 in a preferred embodiment. The organic layer 8 is a known photosensitive organic layer such as PC 335 or PC 405 made by JSR Corporation.
Then, the organic layer 8 is patterned with a form shown in FIG. 4C by the third photolithography process. Halftone exposure is applied in the third photolithography process. This process is the same as the one explained in the third embodiment, and the explanation is omitted here.
In the fifth place, the conductive thin film 9 is formed by a deposition process such as sputtering. In a transmissive liquid crystal display device, ITO or SnO 2 , a transparent conductive film, can be used as the conductive thin film 9 , and the ITO is especially preferable for better chemical stability. ITO 80 nm thick is used as the conductive thin film 9 in a preferred embodiment.
Then, the conductive thin film 9 is patterned with a form shown in FIG. 4D, including pixel electrode, by the fourth photolithography process. This process is the same as the one explained in the third embodiment, and the explanation is omitted here.
In the sixth place, the third metal thin film 11 is formed by a deposition process such as sputtering. This process is also the same as the one explained in the third embodiment, and the explanation is omitted here. Then, the third metal thin film 11 is patterned with a shape of a reflective electrode to form the reflective electrode, by the fifth photolithography process. A configuration shown in FIG. 4E is thereby formed. As described above, in a liquid crystal display device according to the present embodiment of the invention, the reflective electrode 11 and the conductive thin film 9 are formed without having a insulation layer in between.
As explained in the foregoing, the TFT array substrate is formed by five steps of the photolithography process, attaining high manufacturing yields.
FIG. 8 shows a configuration of a semi-transmissive liquid crystal display device according to the fifth embodiment of the present invention. While the configuration can be formed by any of the first to fourth embodiments, the present embodiment will explain a case where the configuration is formed by the first embodiment.
In a liquid crystal display device according to the present embodiment, at least a part of a transmissive electrode in a connection between the first or second metal thin film and the transmissive electrode (the conductive thin film 9 ), that is, in a contact hole formed on the first or second insulation layer, is removed, and the part is covered with the third metal thin film 10 or 11 . The third metal thin film 10 or 11 is connected to both the conductive thin film 9 and the first or second metal thin film.
Connection resistance between the transmissive electrode and the metal thin film through a contact hole is generally higher than connection resistance between the metal thin films through a contact hole. Therefore, in the above configuration, connection resistance between the transmissive electrode and the first or second metal thin film can be reduced.
The configuration explained above makes it possible to reduce connection resistance between the lines and the transmissive electrode on the TFT array substrate to lessen display problems caused by high connection resistance, thereby attaining high manufacturing yields.
FIG. 9 shows a configuration of a semi-transmissive liquid crystal display device according to the sixth embodiment of the present invention. While the configuration can be formed by any of the first to fourth embodiments, the present embodiment will explain a case where the configuration is formed by the first embodiment.
In a liquid crystal display device according to the present embodiment, in a pixel, a periphery of a transmissive electrode (the conductive thin film 9 ) on the organic layer is covered with the third metal thin films 10 and 11 .
An adhesion strength between a transmissive electrode (the conductive thin film 9 ) formed on the organic layer and a metal thin film formed on the transmissive electrode without an insulation layer in between is generally smaller than that between the organic layer and the metal thin film formed directly thereon. The small adhesion causes the problem that the transmissive electrode on the organic layer and the metal thin film formed on the transmissive electrode are separated in course of manufacture. The problem, however, is solved in the configuration according to the present embodiment. It is preferable that the end of the transmissive electrode is inside from the end of the metal thin film by at least 1 μm. The transmissive electrode on the insulation substrate and the metal thin film are properly adhered to each other, and the problem of separation between the transmissive electrode and the metal thin film does not occur in an opening of the transmitting section.
The configuration explained above makes it possible to avoid the separation between the transmissive electrode and the third metal thin film on the TFT array substrate, thereby attaining high manufacturing yields.
From the invention thus described, it will be obvious that the embodiments of the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended for inclusion within the scope of the following claims.
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A semi-transmissive liquid crystal display device is provided with a pixel electrode having in one pixel a reflective electrode reflecting outside light, and a transmissive electrode transmitting light from a back light source, on one of a pair of substrates facing to each other with a liquid crystal film placed in between. The reflective electrode and the transmissive electrode constituting the pixel electrode are formed without having a insulation layer in between. A manufacturing process thereof is simplified by halftone exposure.
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BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention relates to an electrochromic display device and, more particularly, to an electrochromic display device using an organic electrochromic material.
II. Description of the Prior Art
Conventionally, an electrochromic (EC) display device includes a display electrode comprising an EC layer on a transparent conductor film and an opposing electrode, and has a structure wherein a liquid- or solid-phase electrolyte layer is sandwiched between the two electrodes. Both inorganic and organic EC materials are used.
Transition metal oxides such as WO 3 and MoO 3 are known as inorganic EC materials. An inorganic EC material is deposited on a transparent conductor film. When a display electrode of the EC display device using WO 3 is negatively biased, electrons are injected into the WO 3 , so that the display electrode becomes blue. In the device of this type, a material having stable reversible potential must be used as an electrode opposing the display electrode. In general, a symmetrical cell using reduced WO 3 is used. However, the reduced state changes during operation of the device, thus resulting in an unstable display state and low reliability.
A viologen compound, a pyridine compound and a rhodamine compound are known as organic EC materials. A typical example is a device wherein viologen is sandwiched between a pair of electrodes. When the display electrode is negatively biased, viologen is one-electron reduced and is precipitated on the display electrode, so that the display electrode is colored. However, in the device of this type, the anion radical changes over time after precipitation. As a result, the color will not disappear even when the reverse bias voltage is applied, resulting in inconvenience.
As described above, the reversibility of the conventional EC display device is not complete, and the display element has a short life and poor reliability.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide an electrochromic display device which has a long service life and high reliability.
The electrochromic display device of the present invention includes a transparent first electrode and a second electrode opposing the first electrode. An electrochromic layer and an adjoining ionic conductor layer are sandwiched between the first and second electrodes. The electrochromic layer is made of an electrochromic material selected from the group consisting of a naphthalene derivative given by formula (I) below: ##STR1## where X is sulfur (S), selenium (Se) or tellurium (Te), a tetracene derivative given by formula (II) below: ##STR2## where X has the same meaning as given in formula (I), and a fulvalene derivative given by formula (III) below: ##STR3## where X has the same meaning as given in formula (I); and each of R 1 , R 2 , R 3 and R 4 is hydrogen, an alkyl group or an aryl group.
The electrochromic material is preferably formed into a film by vapor deposition under reduced pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of an electrochromic display device according to an embodiment of the present invention;
FIG. 2 is a sectional view of an electrochromic display device according to another embodiment of the present invention; and
FIG. 3 is a schematic view of a deposition apparatus suitable for forming the electrochromic layer of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As previously described, the organic EC material used in the invention is a naphthalene derivative given by formula (I), a tetracene derivative given by formula (II), or a fulvalene derivative given by formula (III).
The electrochromic material of the present invention is one- or two-electron oxidized so as to produce a stable cation radical, thereby changing a visible light absorption characteristic, when a positive voltage is applied thereto. When a negative voltage is applied to the electrochromic material, the cation radical is reduced so that the absorption characteristic of the visible light can be restored. In this manner, the electrochromic display device of the present invention shows stable electrochromic characteristics upon application of forward and reverse bias voltages.
Typical examples of the naphthalene derivatives given by formula (I) are tetrathionaphthalene, tetraselenonaphthalene and tetratelluronaphthalene. The colors of these naphthalene derivatives are green, blue and yellow, respectively. The colors change to yellow, orange and red, respectively, when a voltage of 2 V or more is applied to these derivatives.
Typical examples of the tetracene derivatives given by formula (II) are tetrathiotetracene, tetraselenotetracene, and tetratellurotetracene. The colors of these derivatives are green, blue and yellow, respectively. The colors change to yellow, orange and red, respectively, when a voltage of 2 V or more is applied to the derivatives.
Each of symbols R 1 , R 2 , R 3 and R 4 in formula (III) representing the fulvalene derivative is hydrogen, an alkyl group, or an aryl group. The alkyl group generally has 1 to 5 carbon atoms. The aryl group includes phenyl group or a substituted phenyl group. The substitutent on the phenyl group includes an alkyl group such as methyl group; hydroxyl group; an amino group; and an alkoxyl group (--OR) such as methoxy group. One typical example of the fulvalene derivatives is tetrathiofulvalene. The color of this derivative is yellow and changes to red when a voltage of 2 V or more is applied.
The EC display device of the present invention includes both one utilizing a liquid ionic conductor and one utilizing solid ionic conductors. As shown in FIG. 1, the EC display device using the liquid-phase ionic conductor has a transparent electrode 12 formed on a substrate 11. An EC layer 13 made of the above-mentioned EC material is formed on the transparent electrode 12. A spacer 16 is inserted between an opposing electrode 15 and the EC layer 13, and a sealed space defined by the EC layer 13, the opposing electrode 15 and the spacer 16 is filled with a liquid ionic conductor 14.
A solution of a inorganic electrolyte such as a halogenide (e.g., KCl), a perchlorate (e.g., LiClO 4 ) and a nitrate (e.g., KNO 3 ) may be used as the liquid ionic conductor. Water or an organic solvent such as acetonitrile, dimethylformamide, dimethylacetoamide, propylene carbonate, methanol, ethanol, methylene chloride, acetone, pyridine, and ethylenediamine is used as a solvent of the inorganic electrolyte. The concentration of the solution falls within the range between 0.01 mol % and 10 mol %.
In order to prepare the EC display device, the structure excluding the liquid ionic conductor 14 in FIG. 1 is first obtained. A through hole (not shown) is preformed in the spacer 16. Thereafter, the liquid ionic conductor 14 is injected into the space between the EC layer 13 and the opposing electrode 15 through the through hole. Finally, the through hole of the spacer is sealed.
An EC display element using a solid ionic conductor does not have the spacer 16, as shown in FIG. 2. The structure shown in FIG. 2 is substantially the same as that shown in FIG. 1 except that a solid ionic conductor layer 21 is sandwiched between an EC layer 13 and an opposing electrode 15. The same reference numerals as used in FIG. 1 denote the same parts in FIG. 2. The solid ionic conductor includes the following solid electrolyte.
1. Solid Electrolyte comprising Organic Polymeric Materials and Inorganic Ionic Conductors
It is essential that polymers associated with this electrolyte are formed into transparent films. Examples are polystyrene, polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinyl acetal, phenolic resin, epoxy resin, alkyd resin, acrylic resin (including methacrylic resin), polyacrylonitrile, butadiene-based synthetic rubber, polyolefin, and a mixture thereof.
Examples of the inorganic ionic conductor include cation conductors such as lithium fluoride (LiF), lithium iodide (LiI), lithium hydroxide (LiOH), lithium perchlorate (LiClO 4 ), sodium fluoride (NaF), sodium iodide (NaI), sodium hydroxide (NaOH), sodium perchlorate (NaClO 4 ), and a mixture thereof. The content of the inorganic ionic conductor material preferably falls within the range of 0.01 to 1000% and more preferably the range of 20 to 100% of the weight of the polymeric material. When the content of the inorganic ionic conductor material is less than 0.01% by weight, the color contrast is degraded and the display function becomes defective. However, when the content exceeds 1000% by weight, the compound can hardly be formed into a film, and hence an ionic conductor layer having a uniform composition can hardly be obtained.
The ionic conductor layer of the present invention can contain a pigment for improving the display function (color contrast) and providing an aesthetic effect. Examples of the pigment include white pigments such as titanium dioxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ), yttrium oxide (Y 2 O 3 ), tantalum pentoxide (Ta 2 O 5 ), and silicon dioxide (SiO 2 ); and color pigments such as nickel titanium yellow, cadmium yellow, chromium yellow, cadmium red, molybdenum orange and red iron oxide. Among these pigments, it is preferred to use a white pigment in favor of the aesthetic effect. The content of the pigment with respect to the polymeric material preferably falls within the range of 5 to 50% and more preferably within the range of 10 to 30% of the weight of the polymeric material. When the content of the pigment is less than 5% by weight, the background color can be seen through the display electrode, thereby degrading the aesthetic effect. However, when the content of the pigment exceeds 50% by weight, the formation and ionic condictivity of the ionic conductor material are degraded.
The solid electrolyte containing the polymeric material can be formed on the EC layer 13 by the following process.
The polymeric material is mixed well with the inorganic ionic conductor material at the given mixing ratio. A pigment can also be added to the resultant mixture. If necessary, the mixture is diluted with a proper solvent so as to adjust the viscosity of the mixture. Alternatively, a polymer is diluted before hand for the purpose of the viscosity adjustment. The resultant mixture is applied by spin coating, dipping, roller coating, or spray coating to the EC layer 13. When the solvent is used, the coating is preferably heated at a temperature of 50° to 150° C. so as to evaporate the residual solvent in the film. The solvent for adjusting the viscosity includes nonaqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, cresol, ethyl cellosolve acetate, butyl cellosolve acetate, propylene carbonate, acetonitrile, dimethylacetoamide, N-methylpyrrolidone, dimethylformamide, and a mixture thereof. The degree of the dilution can be properly adjusted in accordance with the coating method adopted. The conditions for coating can be readily determined by a simple preliminary experiment.
2. Solid Electrolyte having Halogen Ionic Conductivity
Solid electrolytes of this type include: lead fluoride (PbF 2 ) or a solid solution of lead fluoride and potassium fluoride (KF); lead-tin fluoride (PbSnF 4 ), a solid solution [(Pb 1-x Sn x F 4 ) where x is 0.25 to 0.75] of lead fluoride and tin fluoride, or a material obtained by substituting part of lead and/or tin of these fluorides with potassium; a material including at least one material selected from the group consisting of rubidium-bismuth fluoride (RbBiF 4 ), potassium-bismuth fluoride (KBiF 4 ), a solid solution [((PbF 2 ) 1-x (BiF 3 ) x ) wherein x is 0 to 0.5] of lead fluoride and bismuth fluoride, lead chloride (PbCl 2 ), tin chloride (SnCl 2 ), a solid solution [((PbCl 2 ) x (SnCl 2 ) 1-x ) wherein x is 0.25 to 0.75] of lead chloride and tin chloride, lead bromide (PbBr 2 ), tin bromide (SnBr 2 ), a solid solution [((PbBr 2 ) x (SnBr 2 ) 1-x ) wherein x is 0.25 to 0.75] of lead bromide and tin bromide, lanthanum fluoride (LaF 3 ), cerium fluoride (CeF 3 ), and lutetium fluoride (LuF 3 ); a complex of crown ether with lithium halogenide; and a ZnF 4 -BaF 2 -X type glass (wherein X is a glass of a mixture of at least one element selected from the group consisting of ThF 4 , LaF 3 , NdF 3 and PrF 3 ).
These materials is preferably formed into a film having a thickness of 200 Å to 1 μm preferably by vapor deposition or sputtering in order to decrease a resistance. However, when the film formed by such a method tends to decompose significantly or to change its composition ratio significantly, or to be degraded in its characteristics by any possible cause, an electrochromic layer can be formed by sintering or solidification on the plate-like solid electrolyte. Alternatively, a solid electrolyte powder having a particle diameter of 0.6 μm to 300 μm can be pressed on the electrochromic layer formed on the electrode.
In any one of the embodiments shown in FIGS. 1 and 2, the EC layer 13 can be formed such that the EC material is dispersed in a polymer and a resultant mixture is applied to the transparent electrode 12 or the solid ionic conductor layer 14. However, it is preferred that the EC layer 13 be directly formed by vapor deposition under a reduced pressure. The vapor deposition can be performed by using the apparatus schematically shown in FIG. 3. The apparatus has a vacuum tank 30. Vapor sources (EC materials) 33 supported by a proper support are disposed below a substrate 31 in the vacuum tank 30. A shutter 32 is disposed between the substrate 31 and the vapor sources 33. The vapor sources 33 are heated by heating power supplies 34. The vacuum tank 30 is kept at a predetermined vacuum pressure by a discharge system 35 including a pump P.
When the EC material is deposited on the substrate 31, the vacuum tank 30 is evacuated by the discharge system 35 and is kept at a vacuum pressure of 10 -7 to 10 -6 torr and preferably at a vacuum pressure of 1 to 5×10 -6 torr. Thereafter, the vapor sources 33 are heated by the power supplies 34 to a temperature falling within a range between about 300° C. and a temperature below the decomposition point of the EC material, and preferably within a range between 300° C. to 400° C. The EC materials 33 are evaporated and are deposited as a thin film on the substrate 31.
The thickness of the EC layer is not particularly limited. The thickness can be easily controlled in accordance with the deposition conditions (e.g., temperature, vaccum pressure, and time). The thickness of the EC layer generally falls within the range of 500 Å to 10 μm.
A deposited or sputtered film of In 2 O 3 , SnO 3 or Au can be used as the transparent electrode 12. A film of the same type may be used as the opposing electrode. However, the opposing electrode can comprise any other film. The substrate 31 preferably comprises a transparent insulator such as glass or polyester.
The EC display device of the present invention has good characteristics such as good response characteristics and good contrast and has a long service life with high stability and reliability.
The present invention will be described in detail by way of examples.
EXAMPLE 1
A transparent electrical conductor film of In 2 O 3 was formed by sputtering on a glass plate, and the conductor film was patterned to allow desirable display. Tetrathiotetracene (general formula (I), wherein X=S) was deposited on the electrode by using a vacuum deposition apparatus at a temperature of 300° to 350° C. and at a pressure of 2.0×10 -6 torr for about 10 minutes, thereby forming an EC layer having a thickness of 5,000 Å. A glass plate having an identical transparent ionic conductor film was used as the opposing electrode. A spacer having an injection hole was adhered by an epoxy sealing agent between the two electrodes so as to form a cell. After the sealing agent was completely hardened, a 0.1M lithium perchlorate solution in propylene carbonate was filled in the space through the injection hole. The injection hole was sealed with a silicone rubber. The electrochromic display element thus prepared was connected to a DC power supply whose polarity could be reversed. A voltage of about 2.5 to 5 V was applied across the electrodes such that the display electrode was kept at a positive potential, and the color of the display electrode changed from green to reddish purple to reddish orange in accordance with the magnitude of the voltage. Even when application of the voltage was stopped, the display color was maintained. When a negative voltage was applied to the display electrode, the color of the display electrode returned to green.
EXAMPLES 2 TO 11
In the same manner as in Example 1, an In 2 O 3 thin film was formed by sputtering on the glass plate and tetrathiotetracene was deposited by vacuum deposition on the electrode.
Meanwhile, 10 ionic conductor compositions shown in Table 1 were prepared. More specifically, polymeric materials were dissolved in proper solvents, and inorganic ionic conductor materials and pigments were added to the resultant mextures in proper amounts, respectively. The inorganic ionic conductor materials and the pigments were sufficiently dispersed by a ball mill and a triple roll mill.
The resultant mixtures were applied to the substrate having the deposited tetrathiotetracene film by dipping, or by spin, spray or roller coating. Subsequently, the substrates were placed on an iron plate heated to a temperature of 100° C. for about 30 minutes, so that the coatings were dried. As a result, uniform, thin ionic conductor films were obtained.
In 2 O 3 was sputtered on the ionic conductor layers to form In 2 O 3 films each having a thickness of 0.2 μm. Thus, opposing electrodes were obtained.
Epoxy resin was sealed in the gaps of the obtained substrates, thereby preparing 10 electrochromic display devices.
TABLE 1__________________________________________________________________________ Inorganic Film coating ionic conductor Pigment conditionsPolymer resin Solvent Type Content** Type Content** Method Film thickness__________________________________________________________________________ (μm)Example 2 polymethyl methyl ethyl LiClO.sub.4 100 TiO.sub.2 20 spinning 2 methacrylate ketoneExample 3 polymethyl methyl ethyl LiClO.sub.4 300 ZrO.sub.2 30 spinning 1 methacrylate ketoneExample 4 polymethyl methyl ethyl LiI 50 Y.sub.2 O.sub.3 30 spinning 1 methacrylate ketoneExample 5 methyl metha- methyl ethyl LiOH 80 TiO.sub.2 20 roller 3 crylate-metha- ketone crylic acid copolymerExample 6 methyl metha- methyl ethyl LiI 40 TiO.sub.2 10 roller 2 crylate-metha- ketone crylic acid copolymerExample 7 polystyrene toluene LiF 100 ZrO.sub.2 10 dipping 1.2Example 8 polystyrene toluene LiClO.sub.4 200 ZrO.sub.2 20 dipping 1.5Example 9 polystyrene toluene LiOH 100 Y.sub.2 O.sub.3 15 dipping 1.5Example 10 polyvinyl toluene LiClO.sub.4 300 TiO.sub.2 10 spinning 2 acetateExample 11 polyvinyl toluene LiF 100 TiO.sub.2 10 spinning 4 acetate__________________________________________________________________________ **The content indicates the content (% by weight) with respect to the polymer resin.
A voltage of 2.5 to 5 V was applied to these electrochromic display devices such that their display electrodes were respectively kept at a positive potential. The color of each of the electrochromic display devices changed from green to reddish orange. When the display electrode of each of the electrochromic display devices was negatively biased, the color thereof immediately changed to green again.
EXAMPLE 12
A substrate was prepared by forming an In 2 O 3 --SnO 2 conductor film on a transparent glass plate. Tetrathiotetracene was deposited thereon at a pressure of 5×10 -6 torr for about 10 minutes, thereby obtaining a tetrathiotetracene film having a thickness of about 5,000 Å. In this case, PbSnF 4 to be deposited was obtained by melting and solidifying PbF 2 and SnF 2 in a platinum melting pot in an inert atmosphere. A tungsten wire was used as the heating wire at the time of deposition. PbSnF 4 was placed in an alumina pot and the tungsten heater was coated with alumina cement, thereby preventing reaction between PbSnF 4 and tungsten. Gold was then deposited on the PbSnF 4 film to prepare an electrode. When a voltage was applied across the In 2 O 3 --SnO 2 film and the gold electrode such that the In 2 O 3 --SnO 2 film was held at a positive potential, the color of the tetrathiotetracene film changed from green to yellowish red. When a negative voltage was applied to the display electrode, the color thereof returned to green. This color change could be repeatedly performed.
EXAMPLE 13
PbSnF 4 prepared in the same manner as in Example 12 was pulverized by an alumina ball mill to obtain a powder having a particle size of 1.5 μm. The powder was sintered by a hot press in a nitrogen atmosphere at a pressure of 1 t/cm 3 and at a temperature of 400° C. to prepare a polycrystalline plate having a thickness of 0.4 mm. Gold was then deposited on one major surface of the polycrystalline plate, and tetrathiotetracene was deposited on the other major surface to a thickness of 1,000 Å. A sintered body obtained by adding 1% of stannic oxide to indium oxide was sputtered on the tetrathiotetracene to a thickness of about 800 Å. The sputtered film and the deposited gold were used as the electrodes. When a voltage of about 2 V was applied to these electrodes, electrochromic characteristics could be observed.
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An electrochromic display device includes a transparent first electrode and a second electrode opposing said first electrode to be spaced apart therefrom. An electrochromic layer is formed in a space formed between the first and second electrodes so as to be in contact with the first electrode. The electrochromic layer is formed of certain naphthalene derivatives, certain tetracene derivatives or certain fulvalene derivatives. An ionic conductor layer is formed in the space so as to be in contact with the electrochromic layer.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is the U.S. National Phase application of PCT International Application No. PCT/FR2011/052285, filed Sep. 30, 2011, and claims priority to French Patent Application No. 1057904, filed Sep. 30, 2010, the disclosures of which are incorporated by reference in their entirety for all purposes.
FIELD OF THE INVENTION
The present invention relates to the field of organic disulphides and polysulphides (subsequently referred to as “organic sulphides”) and more particularly to that of dialkyl disulphides, in particular dimethyl disulphide (DMDS), and in particular to the process for preparing same.
BACKGROUND OF THE INVENTION
Organic sulphides are widely used in a very large number of fields in the chemical industry and in particular the petrochemical industry. In particular, dimethyl disulphide is used as an agent for sulphiding catalysts for the hydrotreatment of petroleum feedstocks, as a feedstock additive for steam cracking, to cite just a few of the possible uses of this compound.
Compared with other products used in these applications, for instance commercial di-tert-alkyl polysulphides, organic sulphides, and in particular DMDS, have many advantages, in particular a high sulphur content (68%) and non-coking degradation products (CH 4 , H 2 S in the case of DMDS). Furthermore, in these applications, DMDS results in performance levels that are generally superior to other commercial products normally used, for example di-tert-alkyl polysulphides.
Among the known methods for the synthesis of organic sulphides, a particularly efficient and economical method is the oxidation of alkyl mercaptans with sulphur, for example for the synthesis of DMDS, the oxidation of methyl mercaptan with sulphur according to the following reaction:
This oxidation of alkyl mercaptans with sulphur, catalysed by organic or inorganic, homogeneous or heterogeneous, basic agents under batchwise or continuous conditions, is accompanied by a release of hydrogen sulphide and also of dialkyl polysulphides (for example dimethyl polysulphides CH 3 S x CH 3 in the case of the synthesis of DMDS) with a sulphur rank x of greater than 2.
In order to manufacture DMDS according to this process of oxidation with sulphur with high yields and a limited production of DMPS (dimethyl polysulphides with a rank greater than 2), patent EP 0 446 109 describes a preparation process comprising two reaction regions interrupted by an intermediate degassing region and followed by a distillation region, in order to eliminate the unwanted by-products.
Although giving a good performance level in terms of yield and selectivity for DMDS, it turns out that this process results in a final product comprising a not insignificant amount of methyl hydrodisulphide (CH 3 SSH). This amount generally varies between approximately 200 ppm and approximately 800 ppm, in particular when high DMDS productivities are sought.
The result of this impurity, which can be considered to be a reaction intermediate, is a slow decomposition over time to give methyl mercaptan and dimethyl trisulphide, by reaction with dimethyl disulphide, according to the following reaction:
CH 3 SSH+CH 3 SSCH 3 →CH 3 SH+CH 3 SSSCH 3
The instability of methyl hydrodisulphide (CH 3 SSH, CAS No.: 6251-26-9) is, moreover, mentioned in the literature by H. Bohme and G. Zinner, in “Justus Liebigs Annalen der Chemie”, 585, (1954), 142-9, in which the methyl hydrodisulphide CH 3 SSH decomposes at ambient temperature, by reacting with itself, to give dimethyl trisulphide and H 2 S according to the reaction:
2CH 3 SSH→H 2 S+CH 3 SSSCH 3
In the case of the synthesis of DMDS by oxidation with sulphur, the very low concentrations of CH 3 SSH do not enable this product to react with itself, and the reaction with the product predominantly present in the medium, DMDS, is highly favoured.
The increase in the methyl mercaptan content in the DMDS makes the synthesis of DMDS described in application EP 0 976 726 not very cost effective, owing to the volatile impurities in the DMDS (traces of methyl mercaptan and traces of dimethyl sulphide (DMS)) which are eliminated in an additional distillation step.
Indeed, its impurities give DMDS a very unpleasant and aggressive odour, which is regarded as a significant cause of trouble during the handling of this product by users.
However, the DMDS obtained, freed of the volatile impurities, still contains traces of CH 3 SSH. In addition, the simple elimination of the impurities by distillation results in considerable DMDS yield losses. This is because CH 3 SSH is much less volatile than methyl mercaptan and than DMS, and has a boiling point of 108° C. very close to that of DMDS (boiling point between 107° C. and 110° C. at ambient pressure). These products (DMDS and CH 3 SSH) are therefore very difficult to separate.
The main objective of the present invention is therefore to provide a process which makes it possible to reduce, or even to eliminate to a very large extent as far as completely, the alkyl hydrodisulphide impurity, for example CH 3 SSH in the case of the synthesis of DMDS.
Another objective of the present invention is a process for eliminating the alkyl hydrodisulphide impurity, without a significant loss of dialkyl disulphide yield.
SUMMARY OF THE INVENTION
One aspect of the present invention relates to a process for treating a reaction crude containing a majority of a dialkyl disulphide obtained by oxidation of at least one alkyl mercaptan with sulphur in an industrial apparatus, in which process said reaction crude is brought into contact with at least one basic catalyst.
According to another aspect, the present invention relates to a process for preparing dialkyl disulphide, said process comprising at least the following steps:
a) oxidation of an alkyl mercaptan with sulphur, by basic catalysis, so as to obtain a first reaction crude containing predominantly the corresponding dialkyl disulphide; b) stripping of the H 2 S formed; c) distillation of the residual alkyl mercaptan; d) separation of the heavy products (polysulphides); e) final topping making it possible to eliminate the last traces of the volatile compounds; f) bringing the stream exiting step a), better still exiting step b), preferably exiting step c), more preferably exiting step d), or exiting step e), into contact with a basic catalyst enabling the elimination of the alkyl hydrodisulphide by conversion of said alkyl hydrodisulphide to dialkyl sulphide or dialkyl polysulphides; and g) recovering of the dialkyl disulphide containing a low alkyl hydrodisulphide content.
Another aspect of the present invention consists of a method of increasing the overall productivity of the industrial synthesis of dialkyl disulphides of formula RSSR, in which R is defined as above, comprising the contacting at least one basic catalyst with the reaction crude of oxidation of an alkyl mercaptan of formula RSH with sulphur.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an industrial apparatus for purifying a dialkyl disulphide synthesis reaction crude.
FIG. 2 is a schematic diagram of an industrial apparatus for purifying a dialkyl disulphide synthesis reaction crude having a catalysis reactor.
DETAILED DESCRIPTION OF THE INVENTION
It has now been found, surprisingly, that the rate of decomposition of alkyl hydrodisulphide in the presence of corresponding dialkyl disulphide can be greatly increased by passage over a basic catalyst of a reaction crude comprising predominantly said dialkyl disulphide.
In the rest of the present description, the expression “reaction crude comprising predominantly a dialkyl disulphide” is intended to mean a reaction medium in which the oxidation of at least one alkyl mercaptan with sulphur has been carried out by basic catalysis.
Preferably, the reaction crude is a reaction crude from which the hydrogen sulphide has been separated (for example by distillation, stripping, and the like). More preferably, the reaction crude is a reaction crude from which the alkyl mercaptan that has not reacted has also been separated (for example by distillation).
Advantageously, the reaction crude is a reaction crude from which not only the hydrogen sulphide and the residual alkyl mercaptan, but also the (“heavy”) polysulphides, and also optionally the traces of alkyl mercaptan and of alkyl sulphide, are separated, for example by distillation.
Thus, a first aspect of the present invention relates to a process for treating a reaction crude containing a majority of a dialkyl disulphide obtained by oxidation of at least one alkyl mercaptan with sulphur in an industrial apparatus, in which process said reaction crude is brought into contact with at least one basic catalyst. The term “alkyl mercaptan” is intended to mean a compound of formula RSH, in which R represents a linear or branched alkyl radical containing from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, and more preferentially from 1 to 4 carbon atoms. The alkyl radical R may also be substituted with one or more groups, which may be identical or different, chosen from halogens, amino, alkylamino, dialkylamino, carboxyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkyl, alkoxy, mercaptoalkyl, alkylthio, alkylcarbonylamino and alkylaminocarbonyl.
Preferably, R represents a linear or branched, unsubstituted alkyl radical containing from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms. In at least one embodiment, the alkyl mercaptan is methyl mercaptan.
The term “dialkyl disulphide” is intended to mean a compound of formula RSSR, in which R is as defined above. In at least one embodiment, the dialkyl disulphide is dimethyl disulphide (DMDS).
The process according to the invention is thus particularly suitable for the synthesis of dimethyl disulphide, without any loss of yield, with elimination of the impurity methyl hydrodisulphide. The elimination of the hydrodisulphide is carried out by means of at least one basic catalyst.
The basic catalyst may be of any type known to those skilled in the art. Said basic catalyst is preferably heterogeneous with respect to the reaction medium, so as to facilitate its subsequent separation. Thus, the basic catalyst may, for example, be chosen from anion exchange resins, such as Amberlyst® A21 from Rohm & Haas, basic catalysts in free amine form, aluminas doped with sodium oxide and/or with potassium oxide, magnesium oxide (MgO), and the like. Preferably, the basic catalyst is an anion exchange resin.
The reaction for basic catalysis of the reaction crude is carried out in a separate step subsequent to the synthesis by oxidation with sulphur. In other words, the reaction crude is used, advantageously after having been subjected to one or more purifications such as those subsequently described, in a further step consisting of a basic catalysis which makes it possible to eliminate the impurity alkyl hydrodisulphide RSSH, in which R is as defined above, in particular CH 3 SSH, without any significant loss of dialkyl disulphide, in particular dimethyl disulphide, yield.
The inventors have in fact discovered, surprisingly, that it is possible to greatly accelerate the rate of decomposition of the alkyl hydrodisulphide, in the presence of the corresponding dialkyl disulphide, in particular the rate of decomposition of methyl hydrodisulphide, in the presence of dimethyl disulphide, in a subsequent and separate basic catalysis reaction.
According to one preferred embodiment, the basic catalyst used for reducing the alkyl hydrodisulphide content, of the reaction crude comprising predominantly alkyl disulphide, is of the same type as, or even is identical to, the basic catalyst used for the reaction for oxidation of the alkyl mercaptan with sulphur so as to give said reaction crude comprising predominantly dialkyl disulphide.
According to another aspect, the present invention relates to a process for preparing dialkyl disulphide, said process comprising at least the following steps:
a) oxidation of an alkyl mercaptan with sulphur, by basic catalysis, so as to obtain a first reaction crude containing predominantly the corresponding dialkyl disulphide; b) stripping of the H 2 S formed; c) distillation of the residual alkyl mercaptan; d) separation of the heavy products (polysulphides); e) final topping making it possible to eliminate the last traces of the volatile compounds; f) bringing the stream exiting step a), better still exiting step b), preferably exiting step c), more preferably exiting step d), or exiting step e), into contact with a basic catalyst enabling the elimination of the alkyl hydrodisulphide by conversion of said alkyl hydrodisulphide to dialkyl sulphide or dialkyl polysulphides; and g) recovering of the dialkyl disulphide containing a low alkyl hydrodisulphide content.
The expression “low alkyl hydrodisulphide content” is intended to mean a content generally less than 50 ppm by weight, preferably less than 10 ppm by weight, more preferably less than 5 ppm by weight.
The process, described above, for synthesis of dialkyl disulphide is particularly suitable for the synthesis of dialkyl disulphide of the general formula RSSR, in which R is as defined above. Said process is entirely suitable for the synthesis of dimethyl disulphide.
Step a) of the process, described above, for oxidation of alkyl mercaptan with sulphur is carried out in a conventional manner known to those skilled in the art. This step is, for example, described in patent application EP 0 976 726. For example, step a) can be carried out under hot conditions and under pressure, for example between 20° C. and 100° C., under 2 to 15 bar, typically, for example, at approximately 70° C., under approximately 6 bar in the case of the oxidation of methyl mercaptan with sulphur.
Steps b), c), d) and e) are included as purification steps, i.e. steps for the at least partial and ideally total elimination of the unwanted by-products present in the reaction crude obtained at the end of step a). More specifically, each of steps b), c), d) and e) corresponds to the elimination of H 2 S, of alkyl mercaptan (starting reactant), of the heavy products, and of the traces of volatile compounds, respectively.
Each of these “purification” steps b), c), d) and e) can be carried out according to any methods known to those skilled in the art, such as stripping, distillation, decanting, and the like.
Step f) for eliminating the alkyl hydrodisulphide, giving dialkyl sulphide or dialkyl polysulphides, corresponds, for its part, to a subsequent and separate chemical reaction carried out in the presence of a basic catalyst, and which can be performed after step a), b), c), d) or e), preferably after step a), b), c) or d), preferably after steps b), c) or d), particularly preferably after step d).
Thus, and according to a particularly preferred embodiment, step f) of conversion by basic catalysis is carried out just before final topping step e).
For the synthesis of dimethyl disulphide, basic catalysis step f) is advantageously performed after heavy product separation step d), i.e. after the heavy product distillation column 6 and before the final distillation column 7 described in FIG. 2 of patent application EP 0 976 726.
Another advantage linked to the process according to the present invention is that it makes it possible to increase the industrial production of dialkyl disulphides. Indeed, in the processes conventionally used today, for example as described in patent application EP 0 976 726, the operator seeks to minimize the formation of organic hydrodisulphide responsible, by self-degradation as indicated above, for the unpleasant odours of said dialkyl disulphides. One means for limiting the formation of hydrodisulphide consists in slowing down the reaction for oxidation of the alkyl mercaptan with sulphur by limiting the rate of introduction of said alkyl mercaptan into the oxidation reaction.
By virtue of the process of the present invention, which consists of adding, to the conventional process, a step of basic catalysis of the reaction crude, enabling conversion of the alkyl hydrodisulphide, it is now possible to increase the rate of introduction of the starting alkyl mercaptan by approximately 30% to 100%. This makes it possible to considerably increase the overall productivity of the industrial synthesis of dialkyl disulphides.
For example, in the case of the synthesis of dimethyl disulphide, the initial flow rate of methyl mercaptan can be increased from approximately 950 g/h (in the conventional process, without basic catalysis for the conversion of the methyl hydrodisulphide) up to approximately 1500 g/h with the additional step of basic catalysis of the reaction crude according to the present invention.
In other words, compared with a synthesis without a “finishing” catalytic reactor, an increase in productivity per m 3 of catalyst (of the main reaction of oxidation with sulphur) from approximately 2000 kg/h/m 3 of catalyst to approximately 3000 kg/h/m 3 of catalyst (of the main reaction of oxidation with sulphur) was observed.
Thus, and according to yet another aspect, the invention consists of the use of at least one basic catalyst on a reaction crude of oxidation of an alkyl mercaptan of formula RSH with sulphur, for increasing the overall productivity of the industrial synthesis of dialkyl disulphides of formula RSSR, in which R is as defined above.
The appended FIG. 1 is a scheme showing an industrial apparatus for purifying a dialkyl disulphide synthesis reaction crude (as described in patent application EP 0 976 726 for the synthesis of dimethyl disulphide, or DMDS).
A degassing column 1 serves to completely eliminate, via the pipe 20 , the H 2 S dissolved in the reaction crude leaving the reactor, via the pipe R. A distillation column 2 makes it possible to separate out most of the alkyl mercaptan (methyl mercaptan in the case of the synthesis of DMDS) in excess with a view to recycling it via the pipe 22 into the oxidation reaction.
On exiting the column 2 , the mixture is brought, via the pipe 23 , into the second distillation column 3 , where the residual dialkyl polysulphides (dimethyl polysulphides in the case of the synthesis of DMDS) are eliminated at the bottom of the column via the pipe 24 so as to be optionally recycled into the oxidation reaction.
The dialkyl disulphide (for example DMDS), collected at the top of the column 3 via the pipe 25 , is introduced into a third distillation column 4 where the volatile impurities, such as methyl mercaptan and dimethyl sulphide (in the case of the synthesis of DMDS) are eliminated at the top of the column via the pipe 26 . The dialkyl disulphide (for example DMDS) is collected at the bottom of the column via the pipe 27 .
The appended FIG. 2 is a scheme similar to that shown in FIG. 1 , with in addition the reactor C for basic catalysis according to the present invention. In FIG. 2 , which represents a preferred embodiment of the present invention, the reactor C enabling the basic catalysis is placed between the column 3 and the column 4 , i.e. after heavy product separation step d) and before final topping step e).
The present invention is now illustrated by means of the following examples, which are in no way limiting in nature for the invention as claimed in the appended claims.
In these examples, the rate of passage over the basic catalyst for conversion of the alkyl hydrodisulphide, which will be referred to as hourly space velocity (HSV), is expressed in h −1 and is equal to the ratio of the hourly space flow rate of reactant to the volume of said basic conversion catalyst.
EXAMPLE 1
Synthesis of DMDS According to EP 0 976 726 with Higher Productivity Conditions, and without Basic Conversion Catalysis (Comparative Example)
a) Equipment:
The appended FIG. 1 is a scheme of the apparatus used, in which a reaction crude results from the reaction for oxidation of methyl mercaptan with sulphur (as described in patent application EP 0 976 726).
A degassing column 1 serves to completely eliminate, via the pipe 20 , the H 2 S dissolved in the reaction crude leaving the reactor, via the pipe R. A distillation column 2 makes it possible to separate most of the methyl mercaptan in excess with a view to recycling it, via the pipe 22 , into the oxidation reaction.
The column 3 makes it possible to separate the residual dimethyl polysulphides (DMPS) with a view to recycling them into the oxidation reactor via the pipe 24 .
b) Procedure:
The methyl mercaptan (MM) is introduced, in the liquid state under pressure with a flow rate of 1440 g/h, into the reactor. The liquid sulphur (S) is introduced with a flow rate of 240 g/h into a first reactor (MM/S molar ratio=4).
The oxidation reactor (reaction volume of 300 ml) contains 20 g of dry Amberlyst® A21 resin. The working pressure is maintained at 5.5 bar relative and the temperature at 40° C. The reaction mixture, on leaving this first reactor, is then sent to a degasser in order to be treated.
After treatment, the mixture, freed of the H 2 S, is sent to a second reactor which contains a charge of 94 g of dry Amberlyst® A21 resin. The pressure in this second reactor is 5.5 bar relative and the temperature is 50° C. On leaving the reactor, the mixture is then introduced into a degasser for elimination of the H 2 S.
On leaving the degassing column 1 , the mixture is introduced into the first distillation column 2 , via the pipe 21 , in order to eliminate virtually all the methyl mercaptan in excess. This methyl mercaptan can be recycled, via the pipe 22 , to the introduction of the reactants into the oxidation reaction. On leaving the column 2 , the mixture is brought, via the pipe 23 , into the second distillation column 3 , where the DMPS are eliminated at the bottom of the column, via the pipe 24 , so as to be optionally recycled into the oxidation reaction.
The DMDS, collected at the top of the column 3 via the pipe 25 , is introduced into a third distillation column 4 , where the volatile impurities such as the methyl mercaptan and the dimethyl sulphide are eliminated at the top of the column via the pipe 26 . The DMDS collected at the bottom of the column via the pipe 27 has the following weight composition (all the values are expressed by weight):
DMDS:
99.9%
DMTS:
334
ppm
CH 3 SSH:
377
ppm
MM:
32
ppm
DMS:
<2 ppm (limit of detection)
This test shows the presence of CH 3 SSH in the final product when the synthesis of the DMDS is carried out under conditions of higher productivity than in Patent Application EP 0 976 726 (higher reactant flow rates and oxidation reactor temperature).
EXAMPLE 2
In Accordance with the Present Invention
Take the DMDS crude above of Example 1 containing 377 ppm by weight of CH 3 SSH. These 337 ppm can give back, over time, 226 ppm of CH 3 SH in the final product.
This DMDS is sent to a bed of Amberlyst® A21 basic resin from Rohm & Haas which has been prewashed with methanol and dried so as to eliminate the water contained in this resin (5 g of dry resin, i.e. 14.3 ml), at a rate of 180 g/h (171 ml/h, which results in an HSV of 12 h −1 ) for 2 hours and at a temperature of 40° C. The CH 3 SSH is no longer detectable by gas chromatography (limit of detection approximately 2 ppm by weight) at the output of the tubular reactor containing the resin.
EXAMPLE 3
Take another DMDS crude, this time containing 428 ppm of CH 3 SSH (these 428 ppm can give back, over time, 257 ppm of CH 3 SH in the final product).
This DMDS is sent to a bed of Amberlyst® A21 basic resin from Rohm & Haas which has been predried (5 g, i.e. 14.3 ml), at a rate of 530 g/h (505 ml/h, i.e. an HSV of 35 h −1 ) for 2 hours and at a temperature of 40° C. The CH 3 SSH is no longer detectable by gas chromatography (limit of detection approximately 2 ppm by weight) at the output of the tubular reactor containing the resin.
EXAMPLE 4
Take a DMDS crude containing 219 ppm of CH 3 SSH (these 219 ppm can give back, over time, 131 ppm of CH 3 SH in the final product).
This DMDS is sent to a bed of Amberlyst® A21 basic resin from Rohm & Haas which has been predried (5 g, i.e. 14.3 ml), at a rate of 1000 g/h (952 ml/h, i.e. an HSV of 67 h −1 ) for 2 hours and subsequently at 2000 g/h (1904 ml/h, i.e. an HSV of 133 h −1 ) for 2 hours also, and at a temperature of 40° C.
At these two flow rates, the CH 3 SSH is no longer detectable by gas chromatography (limit of detection approximately 2 ppm by weight) at the output of the tubular reactor containing the resin.
EXAMPLE 5
Take a DMDS crude containing 239 ppm of CH 3 SSH (these 239 ppm can give back, over time, 140 ppm of CH 3 SH in the final product).
This DMDS is sent to a bed of Amberlyst® A21 basic resin from Rohm & Haas which has been predried (5 g, i.e. 14.3 ml), at a rate of 2000 g/h (1904 ml/h, i.e. an HSV of 133 h −1 ) for 2 hours and at a temperature of 20° C.
The CH 3 SSH is no longer detectable by gas chromatography (limit of detection: approximately 2 ppm by weight) at the output of the tubular reactor containing the resin.
The DMDS used in this example, which initially contained 441 ppm of dimethyl trisulphide (DMTS), contains 809 ppm thereof after passage over the resin, i.e. an increase of 368 ppm. This value of 368 ppm is very close to the theoretical maximum, which is 376 ppm (value which is obtained when considering that each mole of CH 3 SSH has given one mole of DMTS).
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The present disclosure relates to a process for obtaining dialkyl disulphides from alkyl mercaptan and from sulphur, in which a reaction intermediate present in the final disulphide is decomposed at the end of synthesis. This operation makes it possible to avoid the degradation of said reaction intermediate over time, which is responsible for the decrease in purity of the dialkyl disulphide.
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GOVERNMENTAL INTEREST
The invention described herein may be manufactured, used and licensed by or for the Government for Governmental purposes without the payment to the inventor of any royalties thereon.
This application is a continuation-in-part of application Ser. No. 358,946, filed Mar. 17, 1982, now abandoned, which is incorporated by reference herein.
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates in general to the development of submunitions and the stabilization of short, blunt or low fineness ratio bodies, and in particular to a new and useful orientation and stabilization device for a search and destroy armor (SADARM) type submunition which includes a target sensor and a self forging fragment warhead.
SADARM submunitions are known which are intended for release from aircraft or ejected from artillery projectiles. Such devices then search for and destroy vehicular or other targets. The orientation and stabilization devices of the prior art in the SADARM system include a Vortex Ring Parachute. A friction clutch and a first stage decelerator are incorporated to attenuate carrier projectile spin and aerodynamic loading. Additionally, a Ram Air Inflated Device first stage must be configured to disperse the submunitions.
The Vortex Ring Parachute which rotates the submunition at a spin rate which is proportional to the descent velocity, imparts an inherent yawing motion to the assembly and is sensitive to wind. This causes distortion in the scan pattern. Staging is also required so that, in a first stage, deceleration/despin is accomplished to prevent damage to the main stage parachute.
Another technique for generating a scan pattern for a submunition was developed by the AVCO Corp. under the name of SKEET. In this device a rigid arm with tip weight is deployed from the submunition so that the sensing axis of the submunition is tilted with respect to its descent path. With the arm extended a principal axis of inertia of the submunition is aligned at an angle with respect to the cylindrical submunition axis. Thus a steady rotation about a new principal axis of inertia results. Since the arm and tilt weight are relatively small in area, the aerodynamic force acting on them are small. The disadvantage in launching a SKEET type device from a low height of a burst carrier vehicle that has a substantially horizontal velocity component (such as an artillery projectile) is that the spin axis will never be sufficiently close to the vertical to achieve an effective scan pattern.
For a better understanding of the invention, reference is made to U.S. Pat. No. 4,050,381 which discloses a submunition having a target sensor, which is incorporated by reference herein.
SUMMARY OF THE INVENTION
The present invention is an orientation stabilization device for any short, blunt or low fineness ratio body. The present invention is particularly useful as an orientation and stabilization device for a submunition. The orientation device provides steady, near vertical descent and near constant spin such that a scan path on the ground is generated in the form of a logarithmic spiral. To accomplish this it is required that the submunition execute a lunar type motion and that the tilt angle of the scan axes from the vertical be nearly constant.
Specifically the invention comprises a short or blunt body stabilized in flight in a lunar motion primarily by the attachment of a single flexible, tip weighted fin or panel, which causes a rotation of the body about an axis tilted with respect to the horizontal.
The area of the fin according to the invention is small enough to allow direct deployment without recourse to staging or realigning.
Rapid spin deceleration is accomplished by the combination of aerodynamic damping and the conversion of some of the rotational momentum of the artillery projectile to translational momentum when the fin is deployed. This conversion also provides dispersion of the plurality of submunitions deployed from a single artillery projectile or like container.
Accordingly, an object of the invention is to utilize a single rigid or non-rigid panel or fin connected to the short body of a submunition to provide deceleration to a steady vertical descent with a near constant spin rate. The panels or fins are cambered, twisted, swept and tip weighted to give a desired rate of spin and a particular tilt to the body such that the desired sensor scan pattern is achieved.
Another object of the invention is to provide a submunition stabilization and orientation device which does not require staging and which tilts the axis of the submunition, using the aerodynamic moment imparted to the body by a fin, and not by the inertial rearrangement of the submunition caused by the presence of a tip weight at the end of the fin. The fin also supplies sufficient aerodynamic drag and spin damping to vertically orient the spin axis during flight.
A further object of the invention is to provide a device which generates a spiral scanning pattern with small distances between successive turns of the spiral (the so-called lacing distance).
A still further object of the invention is to provide a submunition orientation and stabilization device which is simple in design, rugged in construction, small in volume and economical to manufacture.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is an isometric view of a short cylindrical submunition according to the invention with deployed orientation and stabilization fin;
FIG. 2 is a side elevational view of the device of FIG. 1;
FIG. 3 is a top plan view of the device of FIG. 1;
FIGS. 4a, 4b and 4c is a set of orthogonal views of a non-axisymmetric submunition with deployed orientation and stabilization.
FIG. 5 is an explanatory perspective view showing the orientation of the device according to the invention with respect to the ground, and a spiral scan pattern.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings in particular, the invention embodied therein in FIGS. 1-4c comprises a submunition having a low profile body 1, to which is attached a stabilization and orientation fin 2 with tip weight 4. The fin 2 may be flexible or inflexible and is attached at junction 3 to the body 1. The submunition may be of the SADARM type which includes a target sensor which detects the presence of a suitable target along the axis or a line of sight 5. Such a submunition also includes a self-forging fragment warhead of known design.
The attachment at junction 3 between the cylindrical submunition 1 and its fin 2 allows free movement of the fin about the attachment axis 3. In FIGS. 1-3, the deployment of the tip weight 4 stretches the fin 2 and results in the conversion of rotational momentum to translational momentum. The fin 2 of FIGS. 4a to 4c trails behind the body 1 until the fins 6 cause rotation about the "spin axis". The fin 2 (FIGS. 1-4c) is shaped and tip weight selected such that the centrifugal moment and the aerodynamic moment acting on the fin 2 and the cylindrical body 1 balance when the body 1 is at the desired angle of attach θ. Such an angle is for example, 30 degrees. The junction or line 3 is parallel to a tangent 20 of the cylindrical body 1.
The high drag of the fin 2 rotates the trajectory to a vertical descent. This is shown in FIG. 5 for example. The rotation of the body 1 about a vertical axis 8 thus generates a spiral scan pattern 10 which turns in upon itself as the submunition descends at a velocity V.
Thus, as the submunition 12 falls, a defined area is fully scanned for any suitable target. Once a target is located, the submunition reacts in known fashion to destroy the target.
Referring to FIG. 5, the single fin 2 which extends asymmetrically with respect to the cylinder axis 5 causes the submunition 12 to fly a lunar motion at a constant angle of attack θ. The single fin 2 is sufficiently small so that a maximum number of submunitions can be packed into an artillery projectile. As already noted, the electronics safe and arm device, warhead and parachute are all similar to those which comprise the basic prior art SADARM submunition. The one fin device replaces the parachute that is used in such devices while performing improved orientation and spin functions. Five of the present invention submunitions, for example, can be fitted into an artillery projectile, compared to three prior art submunitions.
The submunition shown in FIGS. 4a-4c may be packaged in a smaller diameter delivery vehicle, a 155 mm artillery projectile for example. The long axis is parallel to the carrier projectile axis of symmetry. A non-axisymmetric (elliptical or oval shaped) self forging fragment warhead is used which spans the flat face 7 and has its center coincident with the scan axis 5. Despin fins 6 are required to rapidly damp the spin rate following ejection from the spinning artillery projectile and to start rotation about the spin axis 8.
The device may include a single fin 2 made of flexible sheet material such as nylon or KEVLAR (a tradename of Dupont Company for a high modulus fiber plastic). The fin connection line may be along either the curved or flat surface of the bodies shown in FIGS. 1 and 4. It also may be tilted (canted) with respect to either face of the body. The leading or trailing edge lines need not be aligned with a diameter of the cylindrical body nor with the long axis of the non-axisymmetric body. These configurational variations, within the bounds of aerodynamic stability, will result in variations in spin rate, descent velocity and sensor axis angle. The tip weight extends the total length of the fin tip. It may be heavier at the leading edge to enhance fin stability. The weight 4 may be chosen for example, to be about 5% of submunition total weight. The proper combination of fabric weave, tip weight configuration and orientation of the connecting line results in the desired camber, twist, sweep and spanwise curvature of the fin that produces lift, drag and stabilization moments appropriate for damping the initial high velocity and spin rate to steady state values. Since the fin on the nonaxisymmetric body is aligned essentially along the initial spin axis, despin vanes are required. These vanes, along with the fin have the effect of turning the angular velocity (spin) vector from alignment with the long axis of the body through an angle of nearly 90° to the scan mode orientation shown in FIG. 5. The body initially rotates about its axis of least inertia. The despin fins damp this rotation and, in combination with the fin cause rotation about the axis of largest inertia.
One preferred embodiment utilizes a 300 mm long, 75 mm wide 475 gm/m 2 KEVLAR (a tradename of Dupont Company for a high modulus fiber plastic) fin with a 0.4 kg tip weight. A fin of this configuration would be suitable for stabilizing a 9 kg submunition similar to the device shown in the FIGS. 1-4. The following performance would be expected:
Terminal velocity: 45 m/sec
Scanning spin rate: 50 cycl./sec
Scan angle: 30 degrees
In FIG. 5 the final steady state scanning portion of the flight is shown. The scanner with a field of view (FOV) of approximately 5° scans the ground plane 14 in a spiral pattern 10. The distance between spiral scans, the lacing distance, is indicated as L D . The spin is shown at P and descending vertical velocity at V. The offset angle θ between the light of sight 5 and the vertical descent path 16 is also shown. The submunition is shown at an altitude Z.
As an example of the operation of the invention, the submunitions of FIGS. 1-3 are ejected from an artillery projectile such as the 8 inch M509, at an altitude of 2,000 to 3,500 feet above ground level. As each submunition clears the base of the projectile (not shown), centrifugal force deploys the fin 2. This force, together with the aerodynamic magnus moment disperses the submunitions so that they are each spaced from the other. The aerodynamic lift and drag and the restoring, pitch, damping, roll and roll damping moments slow the spin and translational velocity to steady state values and stabilize the yawing and pitching motions to very small angles. This allows sensors contained within the submunition to search a circular area with a nearly constant lacing distance.
Described is a samara-type decelerator which drives a submunition in a lunar motion while it descends vertically over a battlefield, scanning for armored target. The decelerator, a one-fin device which consists of a double layer of 3 oz./yd 2 nylon cloth with a tip weight, evolved from the idea of using a single flexible fin with a tip weight to generate a lunar scan motion, which was compared in some respects with the flight of maple seeds (samaras). Aerodynamic testing consisted of flying various configurations of the submunition in a vertical wind tunnel during which a non-dimensional spin-to-velocity ratio pd/2V of 0.110 and a drag coefficient of 3.21 (based on the submunition's diameter) were obtained. A simulation of the observed lunar motion of an axisymmetric model using a rolling body frame, six-degree-of-freedom (6-DOF) computer program and estimates of the aerodynamic coefficients that could not be measured is discussed.
There has been developed, in one aspect, a samara-type decelerator to orient and stabilize scanning submunitions ejected from a spinning projectile in mid to late flight. As was described previously, the submunitions descend vertically over the battlefield, searching for armored targets. A spiral ground-scan footprint pattern is generated by the rotation of the cylindrical submunition about an axis tilted with respect to its axis of symmetry. When a target is detected, an explosively formed penetrator is (almost) instantaneously fired from the front face of the submunition at the detected target.
The samara decelerator includes in one embodiment a single flexible fin approximately 1.5-body diameters long by 0.6-diameters wide with a tip weight (typically between 2% and 5% of the body weight). It is attached to the top of the cylindrical submunition near the edge. The fin is mounted and shaped to give the camber, twist, and dihedral required for steady spin, descent velocity, and stability. Dispersion may be obtained by sequential deployment of the fin on each submunition, each of which is connected to a submunition to be dropped. The packing volume is about 1/10 th that of a deceleration system using a rotating parachute, it has been observed.
The effectiveness of the design can be demonstrated in free-flight testing of a small scale model, using a single flexible fin, in a vertical wind tunnel (VWT) available at a Government facility. Testing with a full dimensional scale model in the VWT can demonstrate a precision planned fall including a constant spin rate, descent velocity, and a scan angle near the design value of 30 degrees. Presented are some results of VWT testing of the samara-body combination. A set of aerodynamic coefficients was estimated and then refined using a six-degree-of-freedom (6-DOF) computer program to simulate the motion observed in the VWT. The wind tunnel model consisted of an approximately full dimensional scale, right circular cylinder made of LEXAN (a tradename of General Electric Company for a polycarbonate plastic) (35% of the weight of an actual submunition) and a single flexible fin as an orientation and stabilization device. The cylinder was 4.75-in. in diameter and 3.40-in. long. The flexible fin was made of a double layer of 3 oz/yd 2 nylon and had a 7.5-in. span and a 3 in. chord. It was attached at the edge of the cylindrical submunition body and weighted at the tip. The tip weight was a steel cylinder with its center of gravity (CG) slightly forward of the mid-chord of the fin. (Subsequent testing showed the fin to be more stable, particularly during the spin up phase, if the CG of the tip weight were located at the quarter-chord position). The model weighed 2.78 lb. and the tip, 0.085 lb. The physical characteristics of the wind tunnel model were evaluated with a computer program capable of calculating moments and products of inertia, center of gravity, mass, and the orientation of the principal axes of inertia for asymmetric bodies. For purposes of modeling, the submunition was treated as a rigid body with three parts: the cylindrical body, the flexible fin, and the tip weight. It was assumed that in flight the orientation of the fin was normal to the spin axis, and the axis of symmetry of the body was tilted at the scan angle (α scan) to the spin axis. A program was run for different values of α scan until the spin axis was aligned with a principal axis of inertia which is the angle about which the body would rotate in the absence of any external moments. The angle for this configuration was 31 degrees. A set of curves can be computed to show the effect of tip weight mass and fin length on the scan angle whether for a LEXAN (a tradename of General Electric Company for a polycarbonate plastic) body; or for an aluminum body. Increasing the tip weight and/or the fin length will increase the scan angle, although plots indicate a maximum angle of about 50 degrees for this size body. The submunition flew at a "steady state" with a velocity of 77 ft/s and angular velocity of 47.1 rad/s as determined from motion pictures. The term "steady-state" is used in a sense appropriate to wind tunnel test conditions. "Steady state" is constant angular velocity about the spin axis and a constant vertical (Z-Earth) velocity. The drag coefficient (C D ) of 3.21 is based on body diameter. Model spin-up as a function of time can be obtained from VWT motion pictures. The moment coefficients C l and the roll damping moment coefficients C l .sbsb.p can be obtained from a computer program which numerically solves the equation: ##EQU1## The resulting C l was 0.282 and the C l .sbsb.p varied between -1.59 and -2.45. After an initial transient period, the cylindrical body flies in a lunar motion at a constant angle-of-attack or scan angle of 25 degrees. The fin was oriented 10 degrees above the horizontal and was curved along the span. The radius of curvature measured from motion pictures was 12 inches. The physical characteristics of the submunition with the fin, in steady-state orientation (35 degrees above the top of the body) were evaluated and the principal axes were found to be rotated by 32 degrees with respect to the body axis of symmetry. The moments of inertia were
I xx =13.65 lb-in. 2
I yy =9.36 lb-in. 2
I zz =15.49 lb-in. 2
I xy =4.39 lb-in. 2
The body was observed to be spinning about an axis 25 degrees off the cylinder symmetry axis rather than at 32 degrees (the direction of the principal axis of largest inertia) due to the external aerodynamic moment acting on the fin. From Euler's equations of motion, this moment is 6.78 in.-lb. A full-weight aluminum submunition is also successfully flown in the VWT.
The flight of the submunition can be modeled by use of a 6-DOF computer simulation. A program is capable of using a body-fixed or fixed plane coordinate system and can handle aerodynamic and geometric asymmetries. To simulate the motion observed in the VWT, a body-fixed coordinate system can be used. The orientation of the body axes with respect to the fixed inertial (Earth) coordinates is described by three Euler angles (ψ, θ, and φ) with ψ the first rotation, θ the second, and φ the third. The body axes (shown aligned with the inertial Earth axes); the positive sense of pitch, yaw, and spin rates, and the Euler angles are noted. The basic aerodynamic coefficients used in the program are defined in an aeroballistic system for symmetric missiles. The presence of the flexible fin on the body, however, makes it highly nonsymmetric. The program can also include terms for aerodynamic asymmetries: the moment coefficients C m .sbsb.o and C n .sbsb.o, and the force co-efficients C Y .sbsb.o and C Z .sbsb.o. The positive sense of the aerodynamic forces and moments are noted. As observed in VWT tests, the body flies at a constant scan angle (angle of attack) of 25 degrees and a constant angular velocity of 47.1 rad/s. A program can be run using initial conditions from a wind tunnel test: initial velocity of 77 ft/s, initial spin rate of 25.1 rad/s and an angle of attack of 0 degrees. This process can be repeated until the transient motion damps out in 2 or 3 seconds and the computed motion will agree with the observed motion. Other combinations of coefficients (C m .sbsb.p, C m .sbsb.o, C n .sbsb.r, C m .sbsb.q) can produce an acceptable match of the wind tunnel results. Scan angle was found to increase with the length of the fin and/or the mass of the tip weight. A set of aerodynamic coefficients can be determined for the submunition which is adequate to simulate the motion observed in a wind tunnel on a six-degree-of-freedom computer program.
While a specific embodiment of the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
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An orientation and stabilization device for a submunition is disclosed. A w profile cylindrical submunition body has a single fin attached thereto at an asymmetrically located position with respect to the central axis of the cylindrical body. The fin is tip weighted in such a way that, when the submunition falls through the air, a constant spin and vertical velocity is established, with the major axis of the cylindrical body disposed at an angle to the descent path.
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RELATED APPLICATIONS
The present utility patent application is based upon Provisional Patent Application Ser. No. 60/047,727, filed on May 27, 1997, and entitled "TABLE GAME", presently pending.
TECHNICAL FIELD
The present invention relates to table games in which a sliding or rolling member is moved across the playing surface of the game. More particularly, the present invention relates to such table games which use paddles so as to provide the propulsive force to the puck member.
BACKGROUND ART
Games in which a light ball is used are known. In one case, the propelling force applied to the ball is created by a player blowing on the ball so as to cause it to travel it in a desired path. In other cases, bats or paddles are used which are suspended from rotary rods that are axially slidable. These rods are provided with radial arms so that animated players manipulate the rotary rods to bring the bat or paddle into engagement with the ball. On the rotation of the bat, a ball engaged thereby is caused to travel to and fro on the table and across the surface or close to the surface thereof. Each player endeavors so as to cause the ball to move in a direction toward the opponent's goal.
In the past, various patents have issued on devices relating to moving a ball across the surface of a table game.
U.S. Pat. No. 3,061,312 teaches a game with a hinged split surface for manipulating a ball back and forth. Pressure is applied to the surfaces so as to allow the surfaces to pivot with respect to one another. A transparent dome or shell 41 extends over the top of the board so as to prevent loss of the ball. The movement of the ball is controlled by a pair of control buttons which are supported on control boxes located outside of the split surface.
U.S. Pat. No. 4,949,967 teaches a game where two inclined surfaces direct a ball back and forth onto propellers/blockers that can be moved from side to side. It does not appear that the board is suitable for being manipulated upwardly or downwardly. The board simply has an incline that assures that the ball will roll from one end to the other upon propulsion by the propeller/blocker members.
U.S. Pat. No. 4,286,785 teaches a game board with two sliding blocker/propellers for passing the ball over a surface with two inclined portions. Once again, the surface is not manipulatable so as to allow for the desired propulsive movement of the ball.
U.S. Pat. No. 3,480,277 teaches a table football game which includes a plurality of rotatable bars extending transversely across a longitudinal axis of a game board. The surface of the game is inclined so that a low point is realized in the center of the board. Handles are provided on each of the bars so as to allow for rotation for the purpose of "launching" the ball toward a goal located at the respective ends of the game board.
U.S. Pat. No. 3,574,350 describes a hockey game apparatus which includes an open box containing a playing field for a puck. A series of parallel spaced apart transverse handles are placed over the playing field. Each handle is axially slidable and pivotable and has sideward extending paddles for striking the puck toward either of an opposing goal puck at each opposite end of the playing field.
U.S. Pat. No. 3,977,675 describes a paddle game apparatus that is provided within a rectangular box. This rectangular box defines a playing area. The playing area has transverse barrier walls of less height than its side and end walls. These transverse barrier walls are spaced from each end wall so as to define goal areas and each barrier wall has an opening to define a scoring pad. Slidable and rotatable paddle-carrying rods extend through the side walls between the barrier walls. The paddles are dimensioned so that a ball may be projected through the opening into a goal area.
U.S. Pat. No. 1,934,381 teaches a table game which has a box-like enclosure with a playing surface of convoluted form positioned thereon. A plurality of bars extend across the playing surface. These bars are manipulatable with handles so as to project a ball from end to end across the playing surface.
U.S. Pat. No. 2,769,638 teaches a simulated hockey game board in which a pair of inclined surfaces are located at opposite ends of the game board. A plurality of propulsion members are located between the center of the board and the net at the end of the board. A spring-like device is provided in the center of the board so as to start the game. The board does not have the capability of being moved upwardly or downwardly in a pivotal manner.
It is an object of the present invention to provide a table game in which the handles and paddles serve to rotate, slide, and change the angle of the playing surface.
It is another object of the present invention to provide a table game which provides greater amusement by the manipulation of the table surface.
A further object of the present invention is to provide a table game which assures continuous action without the need for electrical or pneumatic apparatus.
It is still a further object of the present invention to provide a table game in which the paddle member actually provides three dimensions of action during the propulsion of the puck member.
It is still a further object of the present invention to provide a table game which is easy to use, easy to understand, easy to manufacture, and relatively inexpensive.
These and other objects and advantages of the present invention will become apparent from a reading of the attached specification and appended claims.
SUMMARY OF THE INVENTION
The present invention is a table game that comprises a housing, a playing surface received within the housing, and a paddle means affixed to the playing surface and supported by the housing. The paddle means serves to move the playing surface upwardly and downwardly relative to a vertical force applied to the paddle means. The paddle means is rotatable about the vertical axis relative to an actuation of a handle member connected thereto. The paddle means is resiliently supported in the housing such that the playing surface is urged to a horizontal orientation when a vertical force is not applied.
The playing surface includes a first surface and a second surface which is pivotally connected to the first surface. The paddle means serves to move the first surface independent of the second surface. The paddle means is positioned at one end of the first surface opposite the second surface. A second paddle means is affixed to the second surface and at end opposite the first surface. The second paddle means is resiliently supported by the housing. The second paddle means serves to pivot the second surface relative to the first surface during the application of a vertical force to the second paddle means.
The paddle means includes a frame which is affixed to an end of the playing surface and extends above the top surface, a bar extending across the frame, a paddle member, a vertical member connected to the paddle member and resiliently and slidably connected to the bar, and a handle member affixed to the vertical member. The frame is connected to the housing by a spring. This spring serves to allow the playing surface to move relative to a downward force applied to the handle member. The bar extends between the sides of the housing. The housing has a guide slot formed therein such that the bar extends through the guide slot and moves through the guide slot during the pivotal movement of the playing surface. In particular, the bar includes a first bar which extends in generally parallel relationship to the playing surface, and a second bar in coplanar parallel relationship to the first bar. The vertical member extends between the first and second bars. In particular, the vertical member is retained by a support receptacle slidably affixed to the first and second bars. The support receptacle rotatably receives the vertical member therein. A stop member is affixed to one of the first and second bars so as to limit a slide travel of the support member across the first and second bars.
In the present invention, a puck member is slidably and removably positioned on the top surface of the playing surface. The paddle member supports a first paddle which extends upwardly transverse to the top surface and a second paddle extending upwardly transverse to the top surface. The first and second paddles are in coplanar alignment. The first and second paddles have a space therebetween greater than the diameter dimension of the puck member.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the preferred embodiment of the present invention.
FIG. 2 is a cross-sectional side view of the table game of the present invention.
FIG. 3 is a cross-sectional side view of the table game of the present invention showing the paddle member as pivoting the playing surface.
FIG. 4 is an isolated perspective view of the action of the paddle member.
FIG. 5 is a perspective view of an alternative embodiment of the table game of the present invention.
FIG. 6 is a cross-sectional side view of the table game in accordance with the alternative embodiment of the present invention.
FIG. 7 is an isolated detailed view of the paddle member as used in this alternative embodiment.
FIG. 8 is an isolated see-through view of the operation of the paddle member of this alternative embodiment.
FIG. 9 is an alternative variation of the construction of the paddle member of this alternative embodiment.
FIG. 10 is a cross-sectional view showing the variation of the paddle member of the alternative embodiment.
FIG. 11 is a perspective view see-through view of a second alternative embodiment of the paddle member of the present invention.
FIG. 12 is a perspective view see-through view of a third alternative embodiment of the paddle member of the present invention.
FIG. 13 is a perspective view showing an alternative embodiment of the handle as used with the paddle member of the present invention.
FIG. 14 is an alternative view of the paddle member of the present invention.
FIG. 15 is a perspective view showing the table game of the present invention as incorporated within a video game console.
FIG. 16 is a perspective view of the present invention as shown in operation.
FIG. 17 is another view of the present invention as shown in operation.
FIG. 18 is a perspective view showing the operation of the alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, there is shown at 10 the table game in accordance with the preferred embodiment of the present invention. The table game 10 includes a housing 12 having a playing surface 14 received therein. A first paddle member 16 is affixed to the playing surface 14 and supported by the housing 12. A second paddle member 18 is also affixed to the playing surface 14 and supported by the housing 12. Each of the paddle members 16 and 18 serves to move the playing surface 14 upwardly, downwardly and angularly relative to a vertical force applied to the paddle members 16 and 18, respectively. The first paddle member 16 includes paddles 20 and 22 that are connected to a vertical member 24. The rotation of the handles 26 of the first paddle member 16 serves to cause the paddles 20 and 22 to rotate relative thereto. The second paddle member 18 has a similar configuration.
The playing surface 14 has a generally flat top surface. As will be described hereinafter, the playing surface 14 is pivotal such that the actuation of the paddle members 16 and 18 will cause the playing surface 14 to move angularly upwardly and downwardly. In FIG. 1, it can be seen that a slot 30 is provided so as to allow for the insertion of a puck member 32 during play. The puck member 32 is shown in a trough 34 at the end 36 of the housing 12. The puck member 32 has a plurality of protruding bearings formed therein. These bearings allow the puck member 32 to travel freely and easily on the top surface of the playing surface 14. Alternatively, in the present invention, the puck member 32 can be a ball which rolls along the top surface of the playing surface 14. An alternative slot 38 can be provided on a side wall 40 of the housing 12 so as to allow the puck to be inserted through the side wall.
In FIG. 1, it can be seen that the paddle member 16 has a first handle member 26 and a second handle member 42 extending upwardly vertically from a crossbar 44. The crossbar 44 is affixed to the vertical member 24. The vertical member 24 extends through a guide slot 46 in the top surface 48 of the housing 12. As such, the vertical member 24 can slide in the slot 46 relative to a side-to-side motion imparted upon the handle members 26 and 42 of the paddle member 16.
The paddle member 16 includes a pair of paddles 20 and 22. Each of the paddles 20 and 22 extends vertically upwardly generally transverse to the top surface of the playing surface 14. The surface of the paddles 20 and 22 is generally flat. Each of the paddles 20 and 22 is spaced from each other by a distance greater than the diameter of the puck member 32.
In FIG. 1, it can be seen that the second paddle member 18 extends through a guide slot 50 formed in the opposite end of the housing 12. The second paddle member 18 will have a similar configuration as the first paddle member 16. The paddles 52 and 54 of the. second paddle member 18 face the paddles 20 and 22 of the first paddle member 16. As such, each of the paddle members are in a suitable position for propelling the puck member 32 to and fro.
Legs 56 and 58 serve to support the housing 12 above a surface.
FIG. 2 illustrates the operation and construction of the table game 10 of the present invention. Initially, it can be seen that a frame 60 is affixed to the top surface 62 of the playing surface 14. Frame 60 is affixed to one end of the playing surface 14. A pivot point 64 is formed centrally along the playing surface 14 so as to divide the playing surface 14 into a first playing surface 66 and a second playing surface 68.
The first paddle member 16 has its handle 42 extending upwardly vertically through the guide slot 46 in the housing 12. It can be seen that the frame 60 is connected to the top surface 48 of the housing 12 through the use of spring elements 70 and 72. The paddle 20 is illustrated as standing in a plane transverse to the plane of the playing surface 62. The second paddle member 18 has an identical configuration as the first paddle member 16, but faces in an opposite direction. The puck member 32 is illustrated as positioned on the top surface 62 of the playing surface 14. Another frame 74 is affixed to an opposite end of the playing surface 14 from the frame 60. The frame 74 is also supported by spring element 76.
FIG. 3 shows an operation of the playing surface 14. It can be seen that a downward force 78 is applied to the handle of the second paddle member 18. This causes the second surface 68 of the playing surface 14 to pivot at hinge point 64 relative to the first surface 62. It can be seen that the spring elements 76 are extended by the downward force 78. The spring elements 76 serve to urge the playing surface 68 into a horizontal orientation when the force 78 is not applied to the second paddle member 18. Although the second surface 68 has been pivotted with respect to the first surface 62, the first surface 62 remains in its horizontal orientation. The downward incline of the second surface 68 causes the puck 32 to move toward the paddle 52. As such, the person using the second paddle 18 will receive the puck 32 and can, thereby, project the puck 32 toward the opposite end of the housing 12.
Within the concept of the present invention, it should be noted that the puck member 32 can be any type of object which is suitable for sliding along the top surface of the playing surface 14. For example, the puck member 32 can be a flat puck, can be a puck with bearings, can be a ball, or can be any other object which effectively moves along the surface 14. The spring elements 76 and 72 can be various types of resilient items, such as rubber bands, compression springs, bungie cords, and related items.
FIG. 4 is a detailed view showing the first paddle member 16 and its construction within the housing 12 and relative to the playing surface 14. Initially, it can be seen that the frame 60 is affixed to the playing surface 14. The frame 60 has one portion connected to one side 80 at the playing surface. Another frame portion 60 is connected to an opposite side 82 of the playing surface 14. The frame 60 is mounted within the interior of the housing 12. Guide slots 84 are provided in an inner wall 86 of the housing 12 so as to control the vertical upward and downward movement of the playing surface 14 and the paddle member 16. It can be seen that the paddles 20 and 22 can rotate back and forth relative to the rotation of the vertical member 24. This rotation is accomplished by rotating the handles 26 and 42 relative to each other. The rotation of the handles 26 and 42 causes the crossbar 44 to rotate which, in turn, causes the vertical member 24 to rotate. The vertical member 24 is received by a support receptacle 88 so as to facilitate the rotation of the vertical member 24. The support receptacle 88 is slidably affixed to bars 90 and 92. Bars 90 and 92 extend between the sides of the frame 60. Bars 90 and 92 are arranged in generally parallel relationship to the top surface of the playing surface 14. The bars 90 and 92 are arranged in co-planar parallel relationship to each other. The bars 90 and 92 serve to cause the downward force applied to the handles 26 and 42 to be imparted on the frame 16 which causes the downward deflection and pivoting of the first playing surface 62 relative to the second playing surface 68. A stop member 94 is applied to at least one of the bars 90 and 92 so as to limit the side-to-side travel of the vertical member 24 and the support receptacle 88. This prevents the paddles 20 and 22 from adversely contacting the side walls 86 of the housing 12.
In FIG. 4, it can be seen that the mechanism for the operation of the paddles 20 and 22 allows for three-dimensions of movement. The paddles 20 and 22 can be rotated so as to propel the ball. The handles can cause the paddles 20 and 22 to move from side to side so as to provide defense against the puck passing through the area between the paddles 20 and 22. Finally, the first surface 62 of the playing surface 14 can be deflected downwardly and angularly so as cause the ball to roll towards the paddles 20 and 22.
FIG. 5 shows an alternative embodiment 100 of the table game of the present invention. In this embodiment of the present invention, the housing 102 also receives the playing surface 104 therein. The alternative embodiment 100 utilizes balls 106 as the element for rolling along the playing surface 104 between the paddles 108 and 110. It can be seen that the balls 106 are retained within the ball rack 112. During the playing of the game, the first person to run out of balls within their respective ball rack is the winner of the game.
In this alternative embodiment 100, the handles 114 are connected by a transmission device 120 to the paddles 108. The transmission device 120 is a belt or sprocket driven device which causes the paddles 108 to rotate more quickly or legs quickly relative to the rotation of the handles 114. A detailed description of the transmission device is provided hereinafter.
In the embodiment 100, a tube 122 is provided so as to allow one of the balls 106 to be introduced into the center of the playing surface 104. A hole 124 is provided in a side wall of the housing 102 so as to allow the ball to be delivered to the center of the playing surface from the tube 122. A striker 126 is provided so as to allow the person to properly serve the ball. An alternative tube 128 can be provided when it is desired that the loser serve his or her ball directly onto the paddles 110. A similar arrangement of tubes, and other items, is provided for each side of the game 100. For example, hole 130 is provided so as to allow the introduction of balls from tube 128 on the opposite side of the housing 102. A ball return pocket 132 receives balls from the opposite end of the playing surface 104 so that the ball returns to the player that made the goal. Legs 134 serve to support the playing surface 104 and the enclosure 102 above the floor.
FIG. 6 illustrates the operation of the table game 100. In particular, it can be seen that the playing surface 104 has a first surface 140 and a second surface 142. Springs 144 are interposed between the bottom of the first surface 142 and the floor 146 of the housing 102. Similarly, springs 148 are interposed between the bottom of the second surface 140 and the floor 146. The springs 144 and 148 serve to facilitate the action of the spring elements at the top of the frame. FIG. 6 also shows the ball return tubes 150 and 152 which allow for the return of a ball 154 into a pocket 156 as it passes into a trough 158 at the opposite end of the playing surface 104. The return tube 150 will function in a similar manner relative to the receipt of a ball by trough 160.
FIG. 7 is a detailed view of the operation of the transmission mechanism 120. It can be seen that a belt 162 extends between the vertical member 162 of handle 164 and a sprocket or gear associated with the paddle 110. As such, when the handles 164 are rotated, the gear ratio between the gear 166 associated with the paddle 110 and the gear 168 associated with the vertical member 162 will either enhance or reduce the propulsive effect of the paddle 110.
FIG. 8 shows a similar arrangement as associated with the handles 114 at the opposite end of the playing surface 104. It can be seen that the handles 114 are connected to a vertical member 170. Vertical member 170 extends through the receptacle support 172 so as to be connected to a sprocket 174. Sprocket 174 includes a belt or chain 176. Belt 176 is received by sprocket 178 associated with a vertical member 180 that is connected to the paddles 108. It can be seen that a rapid movement of the handles 114 will cause a more rapid rotation of the paddles 108 by virtue of the gear ratio between the sprocket 174 and the sprocket 178.
FIG. 9 shows an alternative arrangement associated with handles 114 for the transmission of rotation speed from the handles 114 to the paddles 108. As before, the handles 114 are associated with a sprocket 184. Paddles 108 are associated with a sprocket 186. A belt or chain 188 extends between sprocket 184 and sprocket 186. Tension wheels 190 and 192 act on the belt 188 so as to pick up the slack on the belt 188. A lever 194 is associated with the sprocket 184 so as to allow the belt 188 to be adjusted among the various gears found on the sprocket 184. As such, the speed and action of the paddles 108 can be easily adjusted relative to the rotation of the handles 114.
FIG. 10 shows a more detailed view of the arrangement of FIG. 9. It can be seen that the lever 194 extends outwardly of the handle 114 and is supported between bars 200 and 202. Lever 194 is depressed so that it will compress the spring 204 so as to allow the belt 188 to align with the desired gear on the sprocket 184. The tension wheels 190 and 192 are arranged so as to pick up the slack when the belt 184 moves from the larger diameter gear on sprocket 184 to a smaller diameter gear. This arrangement of gears on the sprocket 184 in association with the belt 188 and the sprocket 186 allows the player to adjust the level of difficulty of the game to the desired level.
FIGS. 11 and 12 show alternative arrangements of the configuration of the game of the present invention. In FIG. 11, the embodiment 300 shows handles 302 which are supported on bars 304 and 306. The paddle 308 extends outwardly transversely relative to the direction of the bars 304 and 306. Transmission device 310 serves to impart rotation from the handle 302 so as to cause a "flipping" action of the paddle 308. The arrangement in FIG. 11 can be utilized whenever it is desired to have play along the sides of the game. This can be utilized, for example, if the game is designed for use in doubles.
FIG. 12 shows a similar embodiment as embodiment 300 of FIG. 11. Embodiment 400, as shown in FIG. 12, utilizes a first paddle 402 and a second paddle 404. The short back paddle 404 can be utilized for balance, blocks and for special skill shots.
FIG. 13 illustrates a handle 500 which is configured for safety. It can be seen that handle 500 has a generally rectangular shape. The handle 500 is connected to the vertical member 502. The handle 500 has vertical portions 504 and 506. Horizontal section 508 extends between the vertical sections 504 and 506 so as to prevent injury if a person accidentally falls on top of the handle 500.
FIG. 14 shows another variation on the present invention in which a pair of paddles 600 and 602 can be utilized and supported on the bar 604. Each of the paddles 600 and 602 has an identical configuration. A gripping portion 606 is provided on the paddle 600. A gripping portion 608 is provided on the paddle 602. One of the paddles 600 and 602 can be received by one hand while the other paddle is received by the other hand.
FIG. 15 illustrates the present invention as an arcade video unit 700. In this fashion, the person can play against a machine or against another player.
FIG. 16 shows the present invention 10 as being played by individuals 800 and 802. The individual 800 is gripping the first paddle 16 at one end of the housing 12. The second individual 802 is gripping the handles 18 at the opposite end of the housing 12. As can be seen, the puck 32 is propelled by rotating the handles on the paddle member 16 so as to cause the paddle 20 to propel the puck 32 in the direction of the second individual 802.
FIG. 17 shows a similar arrangement with the table game 10 of the present invention as applied for playing on the floor.
FIG. 18 shows embodiment 100 of the present invention in its actual form for playing.
The present invention is a significant and enjoyable improvement over prior table games in which a puck is propelled from one side of the table to the other. In the present invention, various variations can be made without departing from the spirit of the invention. For example, the playing surface can be arranged in a fixed incline. An electro-magnetic floor can be provided so as to lower friction acting on the ball or puck. This can be arranged such that the ball or puck floats above the playing surface by magnetic or pneumatic force. The side interior walls of the housing can be formed of a membrane so as to allow for a desired bounce during bank shots. The interior of the housing of the present invention can include built-in water tanks so as to weigh the unit down when in use. This prevents the table from moving during play. A tennis-type mesh can be applied to the paddles in place of the solid striking surface. The table can have an octagonal, oval, round or other configuration. A net can be provided over the top surface of the housing instead of glass. The strike surface of the paddle can be curved, flat, rippled, or of other forms.
The present invention also contemplates a double-sized table with four paddles which allow four people to play. This table can contain a partition wall that can be raised with a lever so as to convert the table into two regular tables. The present invention contemplates the ability for one player to control his side of the floor by pushing down but he can also push only on one side of the paddle so as to twist the floor in either direction so that he can direct the ball to the left or right paddle. It is not required that the table move in an even fashion up or down.
There are many configurations of rods or bars that can be used to mount the paddles. For example, one round rod can be used instead of the aforedescribed two bars. One rectangular or other shaped rod can act as a rail so as to prevent the paddle from swinging back and forth while still allowing lateral movement. More than one round rod, i.e. four rods for maximum support of the paddle can be used so as to minimize back and forth movement.
The foregoing disclosure and description of the invention is illustrative and explanatory thereof. Various changes in the details of the illustrated construction may be made within the scope of the appended claims without departing from the true spirit of the invention. The present invention should only be limited by the following claims and their legal equivalents.
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A table game including a housing, a playing surface received within the housing, and a paddle member resiliently affixed to the playing surface and supported by the housing. The paddle member serves to move the playing surface upwardly and downwardly relative to a vertical force applied to the paddle member. The paddle member is rotatable about a vertical axis relative to an actuation of a handle member connected thereto. The paddle member is slidable across a width dimension of the playing surface. The playing surface includes a first surface which is pivotally connected to a second surface. The first surface is independently movable relative to the second surface. A second paddle member is affixed to the second surface at an end of the first surface.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation-in-part application of and claims the priority benefit of patent application Ser. No. 11/675,409, filed on Feb. 15, 2007. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a method for producing a layout of an integrated circuit (IC), and more particularly to a method for producing a layout of an integrated circuit (IC) with radio frequency (RF) devices.
[0004] 2. Description of Related Art
[0005] An IC layout plays an important role in producing an integrated circuit. With the demand of reducing an IC size, it is significant to dispose most devices in a limited area and meet required specifications. However, due to the above concern of the optimization of the area, most IC layout designers at the current stage do not take the IC layout design into consideration as the RF devices e.g. a capacitor, an inductor, and a varactor are included in the IC chip.
[0006] Taking a capacitor for example, designing with a pre-simulation or a post-simulation takes too much time. If the required specifications are not satisfied, a re-design or a change of the layout design is necessary. However, from the viewpoint of efficiency and smart layout design, either the redesign or the change of the layout design is undesired.
[0007] Therefore, what is urgently needed is to develop a method, which is efficient, time-saving, and meets the required specification of designers, for producing a layout of an IC with RF devices.
[0008] In addition, taking a transformer as another example, the layout design for the transformer is based on an electromagnetic (EM) simulation. However, the EM simulation is generally taking a lot of time. Therefore, it is a good way to easily find an exact solution in short time to design the transformer layer based on the EM simulation. As a result, what is urgently needed is to develop a method, which is efficient, time-saving, and meets the required specification of designers, for creating a wide transformer library to quickly find the solution.
SUMMARY OF THE INVENTION
[0009] In view of the above, the present invention is to provide an efficient and time-saving method for producing a layout of an IC with RF devices.
[0010] The present invention provides a method for producing a layout of a device in an integrated circuit before actually fabricated. The method includes inputting at least one fixed parameter for the device for fabrication. And then, a first part of a set of variable parameters of a layout of the device is input. The complete set of the variable parameters is generated. It is checked whether or not the layout with the parameters is satisfying a requirement, wherein an end step is reached if the layout is accepted by the requirement, and a new part of the set of variable parameters as the first part being looping in the foregoing steps if the layout is not accepted by the requirement.
[0011] In order to the make the aforementioned and other objects, features and advantages of the present invention comprehensible, a preferred embodiment accompanied with figures are described in detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a schematic flow chart showing a layout method according to the embodiment of the present invention.
[0013] FIG. 2 is a schematic flow chart showing a layout method according to a capacitor device as the embodiment of the present invention.
[0014] FIGS. 3A and 3B are examples of FIG. 2 , wherein FIG. 3A is a top view illustrating a capacitor, and FIG. 3B is a diagram depicting a frequency response of the capacitor.
[0015] FIG. 4 is a schematic flow chart showing a layout method according to an inductor device as the embodiment of the present invention.
[0016] FIGS. 5A and 5B are examples of FIG. 4 , wherein FIG. 5A is a top view illustrating a spiral-like inductor device, and FIG. 5B is a diagram depicting a frequency response of the spiral-like inductor device.
[0017] FIG. 6 is a schematic flow chart showing a layout method according to a resistor device as the embodiment of the present invention.
[0018] FIG. 7 is a schematic flow chart showing a layout method according to a varactor device as the embodiment of the present invention.
[0019] FIG. 8 is a schematic flow chart showing a layout method according to a transformer device as the embodiment of the present invention.
[0020] FIG. 9 is an example of FIG. 8 , and is a top view of the transformer device.
[0021] FIG. 10 is a schematic flow chart showing a layout method according to an inductor device as the embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0022] FIG. 1 is a schematic flow chart showing a layout method according to the embodiment of the present invention. First, in step S 100 , type information of at least one device is inputted. The device can be a capacitor device, an inductor device, a varactor device, a transformer device, or resistor and a transistor working under RF range. As for the type information of a device, the type information of the capacitor device can be stacked type information of multiple metal layers. The type information of an inductor device can be a shape of the inductor.
[0023] In step S 102 , after a device and required type information are inputted, at least one RF parameter corresponding to the device is inputted. The RF parameter can be an operating frequency and a corresponding Q factor. Besides, considering a frequency response of the device under the radio frequency, a value of the device itself is quite important. For example, a capacitance, an inductance, a resistance are required to be inputted. Next, in step S 103 , a frequency response result is generated according to the RF parameter and the type information of the device. The frequency response result mainly concerns the relation of the device value vs. the frequency and of the Q factor vs. the frequency. If the frequency response result meets the requirements, designers are capable of knowing whether the previously inputted RF parameter meets the requirements of layout design. With the results, it is convenient for designers to design or modify an IC layout.
[0024] In step S 104 , when the frequency response result meets the required specifications, designers can design an IC layout based on the result, so as to make the ultimate IC layout work in the best condition of an operating frequency and a Q factor. However, when the frequency response result does not meet the required specification, the design process returns to step S 102 to input a RF parameter and a geometric parameter again.
[0025] From the above, the main point of the embodiment is that through inputting a RF parameter, a layout design concerns not only the geometric aspects such as an area and a layout disposition, but also the condition under an RF operation. Next, various RF devices are used as different embodiments to further explain the description of the embodiments of the present invention.
[0026] FIG. 2 is a schematic flow chart showing a layout method according to a capacitor device as the embodiment of the present invention. In step S 110 , the type information of the capacitor device is inputted by designers. For example, the type information can be a shape of the capacitor, a stack type of a metal layers, and a number of the stacked type of the aforesaid metal layers. That is, the required geometric structure of the capacitor in an IC design should be confirmed in the beginning. For example, a largest number of the stacked metal layers inputted by designers should be confirmed first.
[0027] Next, in step S 112 , RF parameters of the capacitor device are inputted, such as a capacitance, an operating frequency, a corresponding Q factor, and an area limitation. Besides, information of a bottom electrode and a top electrode of the capacitor, a largest number of the connected capacitors, a length and a width of an area, a finger number of the electrode and a length and a width of the finger are inputted. Thus, the system can proceed with calculations based on the inputted type information of the capacitor and the RF parameters to obtain a corresponding frequency response result.
[0028] The frequency response result can be, for example, the capacitance in response to the operating frequency and the Q factor in response to the operating frequency. Next, in step S 114 , the frequency response result is outputted for the designers. Accordingly, the designers can determine whether the inputted parameter satisfies the requirements of the IC layout and meets the required specifications.
[0029] In step S 116 , when the outputted result in step S 114 meets the required specification, the aforesaid process is finished. On the other hand, if the outputted result in step S 114 does not meet the required specification, the process will return to step S 112 to input a new RF parameter and perform the aforesaid process again until a result meeting the required specification is obtained.
[0030] FIGS. 3A and 3B are examples of FIG. 2 , wherein FIG. 3A is a top view illustrating a capacitor, and FIG. 3B is a diagram depicting a frequency response of the capacitor. In the embodiment, some geometric parameters regarding the capacitor are inputted. For example, the finger number is 12, the finger length is 5 μm, the bottom layer number is 1, the top layer number is 6, and the number of parallel-connected capacitors is 2. Next, a characteristic parameter of the capacitor is inputted. For example, the capacitance is 69.83 fF, the operating frequency Freq is 5 GHz, and the Q factor is 140.
[0031] After the process of inputting, the system performs the calculation process and a result is outputted. For example, in FIG. 3A , the capacitor structure comprises two capacitors connected in parallel each having 12 fingers. In FIG. 3B , the frequency response diagrams of capacitance vs. frequency (C vs. Freq) and Q factor vs. frequency (Q vs. Freq) are respectively shown. The result can help determine whether the required specifications are satisfied. If the result does not meet the required specifications, the parameters can be changed in the process of FIG. 3 to input parameters and perform the process again.
[0032] FIG. 4 is a schematic flow chart showing a layout method according to an inductor device as the embodiment of the present invention. In step S 120 , type information of the inductor is inputted by designers. For example, a shape of the inductor can be spiral, winding, saw-tooth, and square voltage shape. Whether the shape of the inductor is symmetric or whether the inductor is a stacked structure are taken into consideration. That is, the required geometric structure of the inductor in an IC design should be confirmed in the beginning
[0033] Next, in step S 122 , RF parameters of the inductor device are inputted, such as an inductance, an operating frequency, a corresponding Q factor, and an area limitation. Thus, the system can proceed with calculation based on the inputted type information of the inductor and the RF parameters to obtain a corresponding frequency response result.
[0034] The frequency response result can be, for example, the inductance in response to the operating frequency and the Q factor in response to the operating frequency. Next, in S 124 , the frequency response result is outputted for the designers. Accordingly, the designers can determine whether the inputted parameter satisfies the requirements of an IC layout and meets the required specifications.
[0035] In step S 126 , when the outputted result in step S 124 meets the required specifications, the aforesaid process is finished. On the other hand, if the outputted result in step S 124 does not meet the required specifications, the process will return to step S 122 to input new RF parameters and perform the aforesaid process again until a result meeting the required specifications is obtained.
[0036] FIGS. 5A and 5B are examples of FIG. 4 , wherein FIG. 4A is a top view illustrating an inductor device, and FIG. 4B is a diagram depicting a frequency response of the inductor device. In the embodiment, some geometric parameters regarding the inductor device are inputted first, such as shape, symmetric type or stacked type. Next, characteristic parameters of the inductor are inputted, such as an inductance of 2.14 nH, an operating frequency Freq of 5 GHz, and a Q factor.
[0037] After the process of inputting, the system performs the calculation process and a result is outputted. For example, in FIG. 5A , the inductor structure is a symmetric spiral shape. In FIG. 5B , the frequency response diagrams of inductance vs. frequency (L vs. Freq) and Q factor vs. frequency (Q vs. Freq) are respectively shown. The outputted result can help determine whether the required specifications are satisfied. If the result does not meet the required specifications, the parameter is changed in the process of FIG. 4 to input a parameter and perform the process again.
[0038] FIG. 6 is a schematic flow chart showing a layout method according to a resistor device as the embodiment of the present invention. Basically, the resistor does not belong to an RF device. But, the resistor is usually put together with a capacitor and/or an inductor to form an RC, RL, or RLC circuit. Accordingly, when designing a layout of the resistor, not only an area and an arrangement should be taken into consideration, but an effect of a particular operating frequency should be concerned.
[0039] In step S 130 , when designers input type information of the resistor, the type information can be type information of a doped region and a diffusion region. For example, an N-type doped polysilicon, a doped polysilicon, a high-resistance polysilicon, or an N-type diffusion region are inputted. Through the above information, the parameters concerning a position and a size of the resistor can be confirmed. In step S 132 , an operating frequency, a resistance under the operating frequency, and an area limitation are further inputted by the designers. Through the aforementioned two steps, a corresponding frequency response result can be calculated. Next, in step S 134 , a result is outputted for the designers. In step S 136 , based on the outputted result in step S 134 , the designers determine whether the result meets the required specification. When the result meets the required specifications, the process is finished. If the result does not meet the required specifications, the process will return to step S 132 to input parameters again.
[0040] FIG. 7 is a schematic flow chart showing a layout method according to a varactor device as the embodiment of the present invention. A varactor is a variable capacitor whose capacitance can be adjusted. The variable capacitor uses the non-linear dielectric characteristic to dramatically reduce the dielectric constant due to the increase of bias, and can be used for adjusting voltages.
[0041] As for the varactor, the steps are similar to the process described above. First, in step S 140 , type information of the varactor is inputted by designers, such as a N+/N well doped type of a core region and a N+/N well doped type of an input/output region. In step S 142 , parameters such as a varactor value, a Q factor, an operating frequency and an area limitation are inputted.
[0042] In step S 144 , according to the parameters inputted in the aforesaid two steps, a corresponding frequency response result is calculated and outputted by the system. After the result is obtained by the designers, whether the result satisfies the requirements can be determined. When the result meets the required specification, the process is finished. If the result does not meet the required specifications, the process will return to step S 142 to input RF parameters again.
[0043] FIG. 8 is a schematic flow chart showing a layout method according to a transformer device as the embodiment of the present invention. FIG. 9 is an example of FIG. 8 , and is a top view of the transformer device. In step S 152 , designers input type information of the transformer, and then further input RF parameters of the transformer, such as a primary inductance Lp, a secondary inductance Ls, an operating frequency, and a corresponding Q factor (or a ratio of the primary Q factor to the secondary Q factor). The transformer type can be, for example, a turn ratio, an area limitation, an insert loss, and a coupling constant (K), etc. Thus, the system can proceed with calculation based on the inputted type information of the transformer and the RF parameters to obtain a corresponding frequency response result. For example, the inputted parameter can be that inductance Lp/Ls is 2.15 nH/0.9 nH, the Q factor is 7 or more, the operational frequency F is 2.4 GHz, and the transformer is a single-differential type.
[0044] The frequency response result can be, for example, the transformer in response to the operating frequency and the Q factor in response to the operating frequency. In addition, the system can also output turns of primary wires and secondary wires, an outer diameter, a width and a pitch between metal layers. Then, in step S 154 , the frequency response result is outputted for the designers. Accordingly, the designers can determine whether the inputted parameter satisfies the requirements of an IC layout and meets the required specifications.
[0045] In step S 156 , when the outputted result in step S 154 meets the required specifications, the aforesaid process is finished. On the other hand, if the outputted result in step S 154 does not meet the required specifications, the process will return to step S 152 to input new RF parameters and perform the aforesaid process again until a result meeting the required specifications is obtained. For example, above inputted parameters can generate an optimized transformer layer as shown in FIG. 9 , in which the optimized output parameters are that the outer diameter is 150 μm, the primary/second turn number is 2/3, the primary/secondary Q factor ratio Qp/Qs is 9.6/8.4, the primary/secondary inductance Lp/Ls is 2.15 nH/0.92 nH, and the turn ratio is 1.53, etc.
[0046] In each of the aforementioned embodiments, in order to explain briefly, the individual RF device or a device operated under the RF is taken as an example. However, in practice, the IC layout is not limited only to the single type described above. In IC layout, an RC circuit, an RL circuit, and an RLC circuit are usually included, that is, a circuit configuration in combination of capacitors, inductors, and resistors. The layout method of the present invention can be applied to the combined circuit configuration comprising capacitors, inductors, resistors, and other devices mentioned above.
[0047] Besides, the application of the present invention is not limited to the above embodiments, that is, the application is not limited to capacitor, inductor, resistor, and varactor. The layout method of the present invention can be utilized, provided that the layout is applied in the RF range.
[0048] Furthermore, descriptions of the above-mentioned embodiments focus on the layout process for the RF device. The method of the present invention can be combined with the general layout method. In other words, all the device parameters (including the RF device and the non-RF device) are inputted in the beginning. Afterwards, the devices are grouped and arranged on a region where an IC layout will be formed. The portion belongs to the conventional art and will not be explained here. It should be emphasized that any layout method can be operated in coordination with the layout method of the RF device of the present invention.
[0049] Accordingly, based on the disclosure of the present invention, a preferred device search database concerning the RF device is provided. Therefore, time for designers to design the layout diagram can be reduced. Through inputting the parameters of the RF device such as an operating frequency, a Q factor, and an area limitation, an optimized device dimension and a layout design can be obtained. According to the disclosure of the present invention, designers do not require to perform a testing of a frequency response in the layout process, whereas a simulation is carried out by designers in advance in order to perform the layout process only when the required specifications are satisfied. Therefore, time for designers to design a layout diagram can be reduced.
[0050] Further, the invention allows the user to look for the acceptable or even the best layout for the device without actually fabricating the device with the real measurement. A data base has been built, including tremendous amount of solutions of parameters and each of these solutions includes a complete set of parameters comprising later discussed second part and third part parameters. The user can just input some fixed parameters and some rough requirements for some variable parameters. The present invention can then produce the full set of the variable parameters for the layout of the device. The output of the complete set of variable parameters can be checked by the user. Depending on what the device is to be concerned for the layout, the parameter table for input can be divided into three parts, in which the first part is about some fixed parameters for the device type to have layout being searched based on the data base. The first part of fixed parameter includes, for example, the number of metal stack, the intended fabrication processes, and so on, relating to the fixed choice for the device type in structure and fabrication. The second part and the third part are variable parameters, in which some of the parameters can be input by the user and then a complete table can be obtained. The second part of variable parameters, as for example shown in Table 1 for a capacitor, is the option parameters, including the ranges and the intended property. The third part of the variable parameters is related to the actual layout parameters, as for example shown in Table 2 for a capacitor. Usually, at least some of the second part of variable parameters is input by the user, and then the rest parameters of the second part and the third part of the variable parameters can be filled out by the method according to the database in search. Or, at least some of the third part of variable parameters is input by the user, and then the second part and the rest of the third part of parameters can be filled out by the method according to the database in search. It may also include a selection for the optimized choice. However, the user can input any parameter in the second part and the third part as the desired quantity. It can also be noted that the result of the variable parameters as the solution in search for the layout may be different from the original input from the user.
[0000]
TABLE 1
Min. bm
Freq
C/Q
Length/Width
Max. ns
Max. finger_I
Max. nf
Max. array size
[0000] TABLE 2 bm ns Finger_I Nf Array size C/Q Freq.
The parameters in Table 1 are belonging to the parameters of layout in the desired range. Table 2 is the solution of the parameters of the layout of the device type. The parameters in Table 1 are just the examples and are the layout to be searched by the user. For example, the parameter bm is the number m of the bottom metal layer of the device starting from in the metal stack. In this example, the parameter freq is the desired operation frequency. The parameter C/Q is the intended C/Q value. The parameter length/width is the length and width. The parameter Finger_I is a number of fingers of the metal layer.
[0051] Based on the above operation mechanism, the method can be further described in a step flow chart. FIG. 10 is a schematic flow chart showing a layout method according to an inductor device as the embodiment of the present invention. In FIG. 10 , after the process starts, in step S 160 , the fixed parameters relating to the device type are input. In step S 162 , a part of a set of variable parameters is input by the user. Here, the complete set of the variable parameters, as previously described, includes the parameters in Table 1 and Table 2 in two parts. In step S 164 , the complete set of the variable parameters are output based on the solutions in the database. For an additional choice, in step S 166 , and optimal selection can be used to have the optimized solution for the layout under the input criteria if multiple complete sets of variable parameters are output. In step 168 , the output of the parameter of layout is checked by user or an automatic check with the set quantity in S 160 . However, if the layout does not meet the specification then, the process goes back to the step S 162 to search another solution. Otherwise, the process goes to an end. It can be noted that the step S 168 can automatically check for some situation. For example, if the operation frequency is to be checked, then the frequency in table 2 can be automatically checked with the frequency in Table 1 until the frequency range is met. Then, the complete set of layout can be output to the user.
[0052] It can be noted that the foregoing embodiments can be generally applied in FIG. 10 . The invention has built the database with the solutions for the chosen parameters by the user. The layout is not necessary to be actually made with actually measurement. However, the actually layout may be verified with actual fabrication with actually measurement, based on a little modification or no modification on the layout in solution.
[0053] It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.
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A method for producing a layout of a device in an integrated circuit before actually fabricated is provided. The method includes inputting at least one fixed parameter for the device for fabrication. And then, a first part of a set of variable parameters of a layout of the device is input. The complete set of the variable parameters is generated. It is checked whether or not the layout with the parameters is satisfying a requirement, wherein an end step is reached if the layout is accepted by the requirement, and a new part of the set of variable parameters as the first part being looping in the foregoing steps if the layout is not accepted by the requirement.
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[0001] This application is Continuation of U.S. application Ser. No. 10/462,792 filed Jun. 17, 2003. This application claims priority to U.S. application Ser. No. 10/462,792 filed Jun. 17, 2003, which claims priority to Japanese Patent Application No. 2002-284735 filed on Sep. 20, 2002, the contents of which are hereby incorporated by reference into this application.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a semiconductor thin film and a process for production thereof. It is applicable to semiconductor devices including polysilicon thin film transistors (for liquid crystal displays), solar cells, and SOI devices.
[0004] 2. Description of Related Art
[0005] A liquid crystal display has thin film transistors (TFTs) as driving devices. The active layer of TFTs is dominated by polysilicon (poly-Si) film rather than amorphous silicon (a-Si) film, because the former permits carriers (electrons in n-channel and holes in p-channel) high mobility and helps realize smaller cells for a fine pitch display. Another advantage of poly-Si film is the capability of low-temperature annealing by laser. This technique, unlike ordinary annealing that needs a high-temperature process (at 1000° C. or above), prevents the substrate from getting hot during annealing and hence permits TFTs to be formed on an inexpensive glass substrate.
[0006] The laser annealing process is designed to scan a-Si film formed on a glass substrate with an absorbable laser beam, thereby converting a-Si film into poly-Si film. It is one of the important processes used for the production of low-temperature polysilicon thin film transistors. Laser annealing is accomplished by using a pulsed excimer laser (in the form of linear beam) with a wavelength of 308 nm. The linear beam is required to have a uniform intensity distribution over its long axis. With a uniform intensity distribution, the linear beam offers an advantage of achieving annealing with a less number of scans but suffers a disadvantage of requiring more than 20 overlapping shots. A new idea to eliminate this inconvenience has been proposed. It is based on the principle that crystals grow from a low-temperature region to a high-temperature region under the condition that the intensity distribution of the laser beam is spatially controlled. In this way it is possible to obtain polycrystalline silicon composed of large crystal grains by means of low overlapping shots. One way to spatially control the intensity distribution of laser irradiation is reported in Appl. Phys. Lett. 41 (1982) 346. According to this literature, the object is achieved by forming a patterned antireflection film on an amorphous silicon film, thereby controlling the intensity distribution in the amorphous silicon film. The controlled intensity distribution in turn leads to the controlled temperature distribution which promotes the crystal growth in the lateral direction. This known process is laser annealing with CW laser.
[0007] There has been reported a process of irradiation through a phase-shifting mask, in Jpn. J. Appl. Phys. Vol. 38 (1999), pp. L110-112. This process has a disadvantage of giving the phase-shifting pattern which has only one raised and lowered step instead of cyclic steps. As a result, the varying beam intensity gives a non-cyclic pattern on the sample surface and the part with a low intensity remains amorphous. Thus, rendering a sample polycrystalline completely by means of this mask necessitates repeating irradiation on amorphous parts.
[0008] There has been disclosed in JP-A No. 82669/2000 a process of forming polycrystalline silicon film for solar cells. This process is premised on coherent light of plane wave and is designed to convert amorphous silicon into polycrystalline silicon by irradiation with a laser beam through a phase-shifting mask having a cyclic pattern. The disadvantage of this process is that crystallization may be incomplete for tiny crystals in the region where the intensity of irradiation is low.
[0009] There has also been disclosed in JP-A No. 306859/2000 a process for irradiation through a cyclic slit or a cyclic phase-shifting patterned mask. This process has the same disadvantage as mentioned above. That is, tiny crystals remain in the region where the intensity of irradiation is low.
[0010] There has been disclosed in U.S. Pat. No. 6,322,625 and U.S. Pat. No. 6,368,945 and Lamda Physik Corporation's catalog (on Crystal as Optical System, January 2002) a process of irradiating a sample with a laser beam through a mask having a slit pattern which produces a binary pattern intensity distribution. This process, called Sequential Lateral Solidification (SLS) process, consists of repeated crystal growth in the lateral direction in the film by partial laser irradiation and melting to give large crystals. According to this process, the first cycle of irradiation leaves unirradiated regions cyclically and the second cycle of irradiation is carried out with accurate aiming at them
[0011] There is disclosed in Jpn. J. Appl. Phys. Vol. 31 (1992) pp. 4545-4549 a process for irradiation with pulsed laser beams, thereby forming laterally grown crystal regions in a semiconductor film on a substrate. Described also therein is the morphology of the laterally grown crystals. The lateral crystal growth is accelerated by the temperature gradient due to device structure.
[0012] The prior art technologies mentioned above have disadvantages as follows. The process which involves forming a pattern on an amorphous silicon film is limited in throughput because it needs an additional step for pattern forming. The process for forming large crystal grains by irradiation with laser having a cyclically changing intensity distribution suffers the disadvantage of requiring repeated laser irradiation. This is because the first cycle of irradiation leaves some regions (where intensity is low) amorphous or merely forms tiny crystal grains (100 nm or less) due to insufficient energy and hence such incompletely crystallized regions need the second cycle of irradiation. The repeated irradiation needs an accurate stage as explained in the following. One cycle of laser irradiation gives rise to polycrystalline silicon grains whose particle diameter is 1 μm at most if the thickness of amorphous silicon film is 50 nm and the substrate is kept at room temperature. The second and ensuing cycles of irradiation to completely crystallize the remaining amorphous regions need a stage capable of position control accurate to 1 μm or less. Control in the height direction should also be considered in the case where a mask pattern is transferred to the sample surface through a lens so that a cyclic intensity distribution is produced. The pattern transfer is vulnerable to irregularities on the substrate surface on account of the small focal depth. The small focal depth arises from the fact that the lens to achieve an in-plane resolution of about 1 μm needs a lens with a large numerical aperture (NA). In order to ensure a certain focal depth, it is necessary to reduce the area to be irradiated at one time. This in turn makes it necessary to increase the number of frequencies of scanning. For example, in the case of SLS process that employs a lens having a high resolution of 1 μm or less, it is necessary to repeat scanning 30 times to irradiate the entire surface of a substrate measuring 900 mm in width because one region that is covered by irradiation is 30 mm wide. The foregoing is a hindrance to increasing the throughput of the laser annealing process.
SUMMARY OF THE INVENTION
[0013] The present invention was completed in view of the foregoing. It is an object of the present invention to provide a process for efficiently forming a silicon thin film in large area composed of uniform crystal grains whose crystallinity is close to that of single crystals. This object is achieved by the following improvements.
[0014] (1) Use is made of a phase-shifting mask having a periodic pattern scribed at a pitch smaller than four times the maximum particle diameter achievable by crystal growth with one cycle of irradiation. (The maximum particle diameter is about 1 μm in the case where the amorphous silicon film is 50 nm thick and irradiation is performed on the substrate kept at normal temperature.) Irradiation in this manner is illustrated in FIG. 1 . The letter “E” in FIG. 1 indicates that the energy level for irradiation is higher than the threshold value of energy required to bring about crystallization throughout the entire thickness. It is to be noted from FIG. 1 that crystals grow as follows in each cycle of intensity distribution. That is, crystallization takes place first in the part where the energy level is low. (This energy level corresponds to the minimum value of the periodic intensity distribution.) With the lapse of time, the crystal growing position moves gradually toward the part where the energy level is higher. If the minimum energy level is kept higher than a certain value, the resulting crystals would have a particle diameter equal to about one half of the period of the intensity distribution over the entire region of irradiation. In contrast, if the minimum energy level of the intensity distribution is excessively low, crystal growth takes place first at the part where the energy level is higher than the minimum energy level. The result is that there remain regions in which crystallization is incomplete. In order to obviate the necessity of an accurate stage, it is necessary that crystals in the irradiated regions have a large particle diameter and there remain no regions with incomplete crystallization. (Accurate positioning is not necessary unless each shot of irradiation is directed to regions with incomplete crystallization.) This is the difference between the process of the present invention and the conventional SLS process. Incidentally, the restriction “four times” mentioned above arises from the fact that single crystals grow at four places in one cycle. The particle diameter of crystal grains is proportional to the length of period in which temperature decreases and crystals grow. This period depends on the duration of laser pulse, which ranges from 25 ns to 300 ns.
[0015] (2) Use is made of an incoherent optical system. Examples of this optical system include shaped linear beam and homogenized beam. Their use is necessary for reasons explained below. In the proximity method that employs a periodic phase-shifting mask, coherent laser beams give a complex intensity distribution with some peaks (as shown in FIG. 2 ) in place of a simple periodic intensity distribution. One way to eliminate this drawback is by using a homogenizing optical system, in which one laser beam is divided into more than one and each of the divided beams is shaped into a linear beam and finally linear beams are combined together. In this way it is possible to homogenize the intensity in the beam. If this optical system is placed before the mask, it produces a plurality of linear beams entering the mask at different phases and angles. Such linear beams have a simple intensity distribution in place of a complex one with peaks. This simple distribution is schematically illustrated in FIG. 3 . This illustration is verified by electron microscopic observation of a sample which has been prepared by irradiating a substrate with laser beams through a periodic phase-shifting mask placed after the linear beam shaping and homogenizing optical system. The result of observation is shown in FIG. 4 , which is an electron micrograph taken by a scanning electron microscope. The sample for observation was prepared by irradiating an amorphous silicon film with one shot of laser beam (specified below) through a periodic phase-shifting mask with a stripy pattern scribed at a pitch of 2 μm. The laser beam is a pulsed excimer laser beam having a wavelength of 308 nm and a pulse duration of 25-30 ns. The whitish parts in the electron micrograph represent hillocks and correspond to the peaks in the intensity distribution in FIG. 3 . Hillocks occur as the edges of growing crystals crash against each other. A crystal nucleus consists of two regions, one in which the single crystal expands in both directions, and one in which the single crystal is cut by the grain boundary. No hillocks occur in this region. This part differs in appearance from the crystal formed by the SLS method. The mask with a periodic pitch of 2 μm gives rise to single crystals having a particle diameter which is at least 0.5 μm (one quarter of the pitch). Hence there exists no incompletely crystallized region between single crystals. The above-mentioned means forms those crystals which are characterized by hillocks (higher than their surrounding) in a linear row, with their average size (in the direction perpendicular to the row) being about one half of the distance between hillocks. In other words, FIG. 3 should be interpreted to mean that the trough of the intensity distribution corresponds to the crystal nucleus and the crystal grows toward the crest of the intensity distribution. And, hillocks occur at the part where the edges of the growing crystals crash against each other. The average particle diameter of the crystal is one quarter of the mask pitch and one half of the distance between hillocks. Crystal growth in this manner obviates the necessity of repeated irradiation of the incompletely recrystallized region, and this contributes to improvement in throughput. The linear beam shaping and homogenizing optical system produces a light intensity distribution such that the minimum value is not zero on the sample surface and hence does not leave incompletely recrystallized regions. The minimum value of the light intensity distribution can be controlled by varying the intensity of laser beam incident to the mask or by varying the phase difference of the phase-shifting mask. It is established higher than the value which will not leave incompletely crystallized regions.
[0016] (3) Use is made of an optical system to produce a linear beam. The reason for this is that the phase-shifting mask with a periodic stripy pattern (as specified in the present invention) effectively simplifies the intensity distribution when used in combination with the linear beam shaping and homogenizing optical system. The optical system is exemplified by the homogenizing optical system for the laser annealer, available from The Japan Steel Works, Ltd. The linear beam is also used for the ordinary laser annealer that draws on the uniform light intensity distribution. It offers the advantage of reducing the number of cycles of scanning. A disadvantage of linear beam is that the region irradiated with beam ends (in which light intensity is low) tend to become incompletely crystallized. Fortunately, this disadvantage can be eliminated by extending the long axis of the linear beam. In this way it is possible to reduce the incompletely crystallized region that occurs at the overlapped part of scanning. The electron micrograph in FIG. 4 represents a portion of crystals produced by irradiation with a linear beam having a long axis of 365 mm and a short axis of 400 μm. It demonstrates the lateral crystal growth by the linear beam. The foregoing has been realized by the apparatus shown in FIG. 13 . This apparatus consists of the laser annealing unit (of The Japan Steel Works, Ltd.) including the homogenizing optical system and the phase-shifting mask with a periodic stripy pattern. The length established by this is more than 33.5 mm which corresponds to the shorter side of an image display device having a diagonal size of 2.2 inches.
[0017] (4) Laser irradiation is accomplished in such a way that a certain space is retained between the sample and the mask, without any lens placed therein. The reason for this is explained below. The mask has a pitch of order of micrometers, and the lens to resolve this pitch has a short focal depth. Such a lens is vulnerable to substrate irregularities and vibrations, and hence unsuitable for efficient annealing. Any lens immune to the surface irregularities of the substrate being continuously moved by the stage should have a focal depth of more than tens of micrometers. In the case of the proximity method, which uses no lens, the distance between the mask and the sample depends on the pitch of the mask pattern, with no arbitrary values allowed. In fact, the present inventors found that the optimal distance is a multiple of 0.6 mm for a pitch of 2 μm and a multiple of 0.9 mm for a pitch of 3 μm. Unless this condition is satisfied, the periodic intensity distribution is not obtained as desired. It was also found that the margin of the optimal distance is ±30 μm. This implies that the apparatus should have a mechanism to keep the mask-sample distance with an accuracy of ±30 μm.
[0018] (5) Direction of the stripy pattern. The phase-shifting mask should have its stripy pattern arranged approximately parallel to the scanning direction and perpendicular to the long axis of the linear beam. The reason for this is given below. The stripy pattern (consisting of raised and lowered parts) on the phase-shifting mask brings about diffraction in the direction perpendicular thereto. When this direction approximately coincides with the long axis of the linear beam, the diffracted light superposes each other, contributing to the intensity distribution, and the high efficiency is achieved. (In this case, there is a minimum amount of light escaping from the effective irradiating region right under the stripes.) This holds true only when the stripes are approximately parallel to the scanning direction and approximately perpendicular to the long axis of the linear beam. The direction of the stripy pattern will be discussed in more detail in the following.
[0019] (6) Method for reducing the height of hillocks of crystals. Crystals formed by one shot of irradiation have regions with high hillocks as shown in FIG. 4 , and such regions appear at intervals equal to one-half the pitch of the mask pattern. Such hillocks adversely affect the device (for example, causing dielectric breakdown to the gate insulating film of the thin-film transistor), and hence their reduction is desirable. The region of hillocks which is formed by the first shot of irradiation corresponds to the peak position of the light intensity distribution; therefore, the second shot of irradiation should be carried out such that the peak position of the light intensity distribution is displaced from the region of hillocks. In this way it is possible to reduce hillocks. The amount of this displacement should be less than 1 μm. This object is achieved with an ordinary stage whose positioning accuracy is about 5 μm if scanning is carried out in the following manner.
[0020] FIG. 5 shows the relation among the angle (□) between the scanning direction and the direction of the stripy pattern of the phase-shifting mask, the distance (S) over which the substrate stage moves in pulse interval, and the displacement (d) of the peak of light intensity which occurs in pulse interval. The direction of crystal growth is perpendicular to the direction of the stripy pattern, and the position where hillocks are high is displaced by an amount of d=S tan θ. This figure shows the situation in which S is one half of the short axis L of the linear beam or in which laser annealing is accomplished by overlapped irradiation with two shots. In the area where the first shot overlaps with the second shot, hillocks are lower than those in the unoverlapped region. A probable reason for this is as follows. The first-shot irradiation is directed to amorphous silicon for its complete melting, whereas the second-shot irradiation (and subsequent irradiation) is directed to polysilicon. And, polysilicon melts only partly and hence the amount of silicon that moves to form hillocks is less than that results from the first-shot irradiation. Repeating pulse irradiation for the third and fourth shots, with the substrate being continuously moved, efficiently gives rise to a polysilicon thin film of large area having hillocks not higher than 60 nm and having no residual amorphous silicon region. FIG. 6 graphically shows the dependence on angle of the rate of stage movement and the amount of displacement. It is assumed that the laser pulse repeats itself at a frequency of 300 Hz. If the stripy pattern of the phase-shifting mask has a pitch of P μm, then the interval of hillocks formed by each shot is P/2 μm. Therefore, it is desirable that the amount (d) of displacement be smaller than P/2 times 1/(number of overlapping shots). To this end, it is desirable to carry out laser irradiation at an angle which results in the amount (d) of displacement outside the above-mentioned range, while keeping the number of overlapping shots constant or the rate of substrate scanning constant. This is because the particle diameter of crystals varies depending on the number of overlapping shots and hence it is desirable to fix the number of overlapping shots. It is noted from FIG. 6 that the setting of angle ranges from 0.1 to 2 degrees for the practical scanning rate (3 to 60 mm/s). The above-mentioned means permits one to produce a semiconductor thin film characterized by the following. Hillocks higher than the surroundings form in line. The average size of crystals (measured in the direction perpendicular to the line of hillocks) is larger than 0.4 μm. There is an angle of 0.1 to 2 degrees between one side of the substrate on which the polycrystalline silicon film is formed and the direction of the line of hillocks. Moreover, laser annealing by the above-mentioned means causes hillocks to form in line which are higher than the surroundings and lines of hillocks exist periodically, with the average distance between them varying. This is seen from the state of crystallization in the region in which the first irradiation overlaps with the second irradiation, as shown in FIG. 5 . Thus, it is possible to form a semiconductor thin film which is characterized in that there exist no amorphous region between hillocks. FIGS. 17, 18 , and 19 respectively show the array of hillocks resulting from one-shot irradiation without overlapping, two-shot irradiation with overlapping, and four-shot irradiation with overlapping. The above-mentioned method may be applied to the slit SLS method which employs the periodic pattern.
[0021] Another method for reducing hillocks is mentioned in the following. Annealing is carried out first by using the mask, and then ordinary pulse irradiation is carried out, to reduce hillocks, without the mask or by using that part of the mask which is not patterned. FIG. 7 is an electron micrograph (taken by a scanning electron microscope) of the crystals which have been obtained by a first shot of irradiation through a phase-shifting mask having a stripy pattern scribed at a pitch of 2 μm and a second shot of irradiation without the mask. It is noted that the sample shown in FIG. 7 has particle diameters of about 0.5 μm in two directions whereas the sample shown in FIG. 4 has particle diameters of about 0.5 μm only in one direction perpendicular to the stripy pattern of the mask. The effect of the above-mentioned procedure is that the height of hillocks decreases from 90 nm to 70 nm (in terms of PV value). This effect is more remarkable as the number of shots of irradiation without the mask increases.
[0022] (7) Method of irradiation. According to the process of the present invention, one shot of pulse irradiation is enough for complete conversion of amorphous into crystalline within the irradiated region covered by the width of the laser beam. This obviates the necessity of taking accurate aim in the subsequent pulse irradiation. Therefore, it is not necessary for the stage to have a feeding accuracy of about 1 μm. In addition, the process of the present invention does not use the transfer system which needs a lens having a large NA for resolution of several micrometers in irradiation with a periodic intensity distribution of several micrometers. This eliminates the necessity of auto-focusing with a precision of several micrometers at each time of shot because the gap has a large margin. Experimental results indicate that the height margin is ±30 μm. This large margin reduces the effect due to up and down vibration and variation of substrate thickness.
[0023] For reasons mentioned above, the mask according to the present invention can be incorporated as such into the ordinary laser annealing apparatus. For example, it can be built into the laser annealing apparatus (made by The Japan Steel Works, Ltd.) which has been developed for annealing with the ordinary uniform light intensity distribution. The linear beam in this case measures 365 mm in long axis and 400 μm in short axis. The mask designed for this particular apparatus measures 400 mm long and 20-50 mm wide. The advantage of using a linear beam is that a wide area can be annealed by one scanning. Scanning with a linear beam for annealing may be accomplished in the direction as shown in FIGS. 8 and 9 . Scanning may also be accomplished in mutually perpendicular directions as shown in FIG. 10 . The advantage of this scanning method is that crystals grow in two directions and hence the resulting crystals have large particle diameters extending in two dimensions. Such crystals provide high mobility in any direction.
[0024] The following is concerned with parallelism of the scanning direction to the side of a substrate. It is assumed that a linear beam is scanned in the direction approximately parallel to the long side of a glass substrate measuring 730 mm by 920 mm. If the linear beam is aslant 0.1 degree with respect to long side of the glass substrate, scanning over a distance of 900 mm causes a displacement of 2 mm to occur in the short side. This means that an area of 4 mm is left unirradiated at both short sides of the substrate. In addition, usually the amorphous silicon film is thin in the peripheral region of the substrate. The thin region is about 10 mm from the edges of the substrate, depending on the performance of the CVD apparatus used to form the amorphous silicon film. Thus, the region of about 14 mm from the edges of the substrate is wasted. Common practice to minimize the wasted area is to make the angle between the scanning direction and the side of the substrate smaller than 0.1 degree. Moreover, it is also common practice to ensure parallelism when a large single substrate is cut into many small semiconductor devices. Therefore, the direction of scanning should have an accuracy within 0.1 degree with respect to one side of a large substrate and a small cut device. Thus, it is not necessary to distinguish between the direction of scanning and the direction of one side of the substrate. By combining the above-mentioned means (1) to (7), it is possible to form a semiconductor thin film which is characterized by the following.
[0025] The semiconductor thin film has hillocks in line which are higher than the surroundings.
[0026] The hillocks have an average size larger than 0.4 μm measured in the direction perpendicular to the direction of their line.
[0027] The direction of hillocks' line is aslant 0.1 to 2 degrees with respect to one side of the substrate on which polysilicon film is formed.
[0028] The above-mentioned means may also be applied to the slit SLS method which employs the periodic pattern.
[0029] (8) Measure to prevent the sticking of silicon vapor. A laser beam used for crystallization by laser annealing has energy sufficient to melt and even evaporate silicon. The resulting silicon vapor sticks on the mask, thereby reducing the intensity of laser beam and hampering crystallization. Thus, it is necessary to introduce a measure to prevent the sticking of silicon vapor. This object is achieved by forming a gas flow in the vicinity of the mask surface, as shown in FIG. 11 . It is desirable to use the same kind of gas as introduced into the laser annealing chamber so that the gas flow does not adversely affect crystallization. The above-mentioned means may also be applied to the slit SLS method which employs the periodic pattern.
[0030] (9) Increasing the process margin against the fluctuation of laser intensity. When a laser used for irradiation through a patterned mask has an excessively low intensity, there occurs an undesirable situation in which the irradiated region where the intensity is lowest remains amorphous. Such a situation can be avoided by repeating irradiation twice, the first one without a mask and the second one with a mask. In this way crystallization takes place throughout the irradiated region regardless of the intensity distribution, and hence there remain no amorphous regions or microcrysalline regions.
[0031] (10) Mask patterns that can be used in common for the proximity method. The mask with a periodic stripy pattern is under restrictions by the relationship between the stripe pitch and the gap when it is used for the proximity method. For a phase-shifting mask having a stripy pattern, the gap should be a multiple of 0.6 mm or 0.9 mm if the pattern pitch is 2 μm or 3 μm, respectively. This means that either of the two pitches (2 μm and 3 μm) can be used if the gap is 1.8 mm. In other words, the pitch of the periodic stripy pattern should be a multiple of 1 μm, if it is to be applied to the same gap. The pattern meeting the above-mentioned requirements permits one to produce a polycrystalline semiconductor thin film which is characterized in that hillocks form in line which are higher than the surroundings, there are regions in which the array of hillocks has different periodicity, and the periodicity of array is a multiple of the gap. The above-mentioned means may also be applied to the slit SLS method which employs the periodic pattern.
[0032] (11) Arrangement of elements in a device. The process according to the present invention yields crystals whose particle diameters are oriented in one direction. Since the carrier mobility is large in this orienting direction, the resulting transistor has improved characteristics if the source-drain direction is made to coincide with this direction. It is possible to make the source-drain direction incline 0.1-2 degrees with respect to one side of the substrate if the above-mentioned method for reducing the height of crystal hillocks is combined with the above-mentioned scanning method. If the source-drain direction is perpendicular to the crystal growth direction, the resulting transistor is poor in characteristics. For transistors in which there are mutually perpendicular source-drain directions, it is possible to cancel out each other different characteristics due to different source-drain directions if the scanning direction is aslant about 45 degrees with respect to the crystal growing direction.
[0033] (12) Application to SOI structure. The SOI (silicon on insulation) structure is composed of a single-crystal silicon wafer and each of oxide film and silicon film sequentially formed thereon. It is obtained by three steps as follows. Heat treatment on the surface of a silicon wafer to cover it with a thermal oxide film about 5 μm thick. Chemical vapor deposition (CVD) to deposit an amorphous silicon film on the oxide film. Laser annealing of the amorphous silicon by the process of the present invention. These steps do not require lamination. Incidentally, the thermal oxide film mentioned above may be replaced by a CVD oxide film. The thus formed SOI structure is used to fabricate semiconductor devices.
[0034] By using the above-mentioned means, it is possible to produce a semiconductor device which is characterized by the following.
[0035] The substrate on which the semiconductor device is formed has an uppermost layer of polycrystalline silicon. The polycrystalline silicon film has hillocks in line which are higher than the surroundings.
[0036] The hillocks have an average size larger than 0.4 μm measured in the direction perpendicular to the direction of their line.
[0037] The direction of hillocks' line is aslant 0.1 to 2 degrees with respect to one side of the substrate on which the polycrystalline silicon film is formed.
[0038] In addition, by using the above-mentioned means, it is also possible to produce a semiconductor device which is characterized by the following.
[0039] The substrate on which the semiconductor device is formed has an uppermost layer of polycrystalline silicon. The polycrystalline silicon film has hillocks in line which are higher than the surroundings.
[0040] The average particle diameter measured in the direction perpendicular to the direction of line is larger than the intervals of the hillocks.
[0041] (13) Laser annealing with CW laser is explained below. It is possible to form a polycrystalline thin film composed of large crystals grown in the lateral direction without the necessity of forming a patterned antireflection film on an amorphous silicon film if an amorphous silicon film formed on a glass substrate is irradiated (by scanning the glass substrate) with CW laser (in the form of linear beam) through a phase-shifting mask having a periodic stripy pattern. In this case, the stripy pattern of the phase-shifting mask should preferably be oriented in the direction approximately perpendicular to the direction of the long axis of the linear beam and also oriented in the direction approximately parallel to the scanning direction. The stripy pattern of the phase-shifting mask may have a larger periodicity than that used for the pulsed laser mentioned above. In practice, the periodicity may be one to tens of micrometers. The reason for this is that scanning with CW laser is more flexible than scanning with pulsed laser for adjustment of the length of time in which molten silicon cools for crystal growth. Scanning with CW laser also needs as accurate control over the mask-sample gap as in scanning with pulsed laser. The direction of scanning should be aslant a certain angle with respect to the direction of the stripy pattern of the phase-shifting mask. If this angle is zero and the minimum value of intensity distribution is insufficient for crystallization, the amorphous silicon film remain amorphous or microcrystalline along the direction of scanning. In order to avoid this situation, it is necessary to make a certain angle between the direction of scanning and the direction of the stripy pattern of the phase-shifting mask. This angle (□) should be determined so that sin □>P/(2W) is satisfied, where W denotes the width of the short axis and the P denotes the pitch of the stripy pattern. Scanning in this manner causes the insufficiently crystallized region to overlap with the sufficiently crystallized region and hence eliminates the insufficiently crystallized region.
[0042] The CW laser should have a wavelength of 532 nm, preferably shorter than this, because silicon absorbs laser light more easily and melts with less energy as wavelengths decrease. The CW laser that can be used in this process is YAG laser having wavelengths of 532 nm and 266 nm as the second and higher harmonics or Ar-ion laser having a wavelength of 488 nm or 514.5 nm.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a diagram showing how crystallization takes place by one-shot irradiation when the mask pattern is used according to the present invention;
[0044] FIG. 2 is a diagram showing the result of numerical analysis of the intensity distribution in the case of irradiation with coherent light through a mask pattern;
[0045] FIG. 3 is a schematic diagram showing the intensity distribution in the case of crystallization (according to the present invention) by irradiation with incoherent light through a mask pattern;
[0046] FIG. 4 is an electron micrograph (taken by a scanning electron micrograph) of crystals formed by one-shot irradiation according to the present invention;
[0047] FIG. 5 is a schematic diagram showing the relation among the scanning direction, mask pattern, and laser beam in the present invention;
[0048] FIG. 6 is a diagram showing the relation among the angle between the scanning direction and the mask pattern and the rate of scanning in the present invention;
[0049] FIG. 7 is an electron micrograph (taken by a scanning electron microscope) of an example of the crystals formed according to the present invention;
[0050] FIG. 8 is a diagram showing an example of the scanning method that can be used for crystallization in the present invention;
[0051] FIG. 9 is a diagram showing an example of the scanning method that can be used for crystallization in the present invention;
[0052] FIG. 10 is a diagram showing an example of the scanning method that can be used for crystallization in the present invention;
[0053] FIG. 11 is a schematic diagram showing how to cope with the clouding of the mask;
[0054] FIG. 12 is a diagram showing the relation between the direction of crystals and the source-drain direction of a thin-film transistor fabricated;
[0055] FIG. 13 a diagram showing an example of the apparatus used for crystallization according to the present invention;
[0056] FIG. 14 is a schematic diagram showing how to cope with the clouding of the mask;
[0057] FIG. 15 is a diagram showing the relation among the beam width of CW laser, the stripy pattern of the phase-shifting mask, and the direction of scanning;
[0058] FIG. 16 is a graph showing the relation among the beam width of CW laser, the pitch of the stripy pattern of the phase-shifting mask, and the angle between the stripy pattern and the scanning direction;
[0059] FIG. 17 is an array pattern of silicon hillocks resulting from pulse laser annealing by scanning with one-shot overlapping;
[0060] FIG. 18 is an array pattern of silicon hillocks resulting from pulse laser annealing by scanning with two-shot overlapping; and
[0061] FIG. 19 is an array pattern of silicon hillocks resulting from pulse laser annealing by scanning with four-shot overlapping.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0062] The invention will be described in more detail with reference the following examples.
Example 1
[0063] The laser annealing process according to the present invention is accomplished by using an apparatus shown in FIG. 13 . There is shown a sample substrate 1 having an amorphous silicon film formed thereon. There is also shown a mask 2 which is placed 0.6 mm above the substrate 1 . This mask is a periodic phase-shifting mask with a stripy pattern scribed at a pitch of 2 μm. (An enlarged side view of the substrate 1 and the mask 2 is shown in FIG. 1 .) There is shown a pulsed laser beam 3 specified below.
[0000] XeCl excimer laser generated by Model STEEL 1000 of Lamda Physik Corporation.
[0000] Wavelength: 308 nm
[0000] Pulse intervals: approx. 27 ns
[0000] Repeating frequency: 300 Hz
[0064] The laser beam 3 is shaped into a linear beam, 365 mm in long axis and 400 μm in short axis, by an optical system consisting of a homogenizer 7 (from Micro Las Corporation) and cylindrical lenses 6 and 5 . There is shown a substrate stage 4 which feeds the substrate at a prescribed rate during laser irradiation. The substrate stage 4 moves with a positioning accuracy of 5 μm. In the case of irradiation with two overlapping shots, the linear beam advances in one cycle of 300 Hz a distance equivalent to half the short axis of the linear beam (or 400 μm). For the linear laser beam to advance 200 μm within 1/300 seconds, the scanning rate should be 60 mm/s.
[0065] There is a sensor (not shown) to monitor the gap between the mask and the substrate. The sensor controls a piezo-actuator to keep the gap at 600±30 μm. The gap sensor and piezo-actuator are installed at both ends of the long axis of the mask jig.
[0066] Scanning with the laser beam is carried out in parallel directions as shown in FIG. 8 or 9 , or in mutually perpendicular directions as shown in FIG. 10 .
[0067] The direction of scanning is aslant 0.15 degrees with respect to the direction of the stripy pattern of the mask. For the scanning rate of 60 mm/s, this angle causes the crystal pattern on the substrate to shift 0.5 μm, as shown in FIG. 6 . This amount of shift is just adequate for the hillocks formed by the first shot to be reduced by the second shot, because hillocks occur at intervals of 1 μm in the case of scanning through a phase-shifting mask with a pitch of 2 μm.
[0068] Annealing in the above-mentioned manner takes about 15 seconds for the entire surface of a substrate measuring 730 mm by 920 mm. This annealing is about 10 times as efficient as ordinary annealing by laser irradiation with a uniform intensity distribution, because ordinary annealing needs overlapped irradiation with 20 shots or more in order that the resulting crystal grains are larger than 0.3 μm. In addition, annealing in the above-mentioned manner offers the advantage of giving rise to larger crystal grains (0.5 μm), which should be compared with crystal grains (0.3 μm) in the case of ordinary annealing. Large crystal grains help increase the carrier mobility, thereby improving the device characteristics. Incidentally, the same result as mentioned above may be obtained even in the case where scanning is carried out in one shot (without overlaps) or in more than two shots (with multiple overlaps).
[0069] The pulsed laser to be used for annealing should meet the following requirements for wavelength and energy density.
[0070] {(Absorption coefficient of amorphous silicon at wavelength of concern)×(Reflectivity of amorphous silicon at wavelength of concern)}/{(Absorption coefficient of amorphous silicon at wavelength of 308 nm)×(Reflectivity of amorphous silicon at wavelength of 308 nm)}>380 mJ/cm 2 . For a laser beam with a fixed pulse energy, it is necessary to change the area of irradiation so that the energy density meets the above-mentioned requirements. The pulse intervals should preferably be 27 ns and above. In addition to the above-mentioned excimer laser, a solid-state laser with a wavelength of 532 nm or below can also be used.
Example 2
[0071] This example uses the same equipment as in Example 1 but differs in the way of irradiation. In this example, irradiation may be carried out in two steps. Irradiation in the first step is through a mask pattern as with the foregoing embodiment, and no mask pattern is used for irradiation in the second step. Irradiation in this manner yields a thin film consisting of isotropic crystal grains and having low hillocks. Alternatively, irradiation may be carried out such that no mask pattern is used in the first step and a mask pattern is used in the second step. The effect of irradiation in this manner is that the second step (with a mask pattern) ensures crystallization at the part where the light intensity is very low. This effect permits the process to be run with low laser energy.
Example 3
[0072] This example uses the same equipment as in Example 1 except for the phase-shifting mask in which the stripy pattern has a pitch of 3 μm. In this example, the mask is 0.9 mm away from the substrate and the rate of scanning is 30 mm/s for 4-shot overlapping. Scanning is carried out in a direction which is aslant about 0.17 degrees with respect to the mask so that the shift of the pattern is 0.2 μm as shown in FIG. 6 . This is because the interval of hillocks is 1.5 μm and hence the shift should be smaller than 0.325 μm (1.5 μm divided by 4) for 4 shots on the same spot. Thus, repeating overlapping shots four times with a specific amount of shift reduces hillocks.
Example 4
[0073] This example demonstrates how to protect the mask from being clouded with silicon vapor. (The mask is exposed to silicon vapor during irradiation.) The object is achieved by flowing nitrogen gas along the upper and lower surfaces of the mask 2 , as shown in FIG. 11 (sectional view). The mask is held by a frame which has a number of holes to blow nitrogen gas from one side and a number of holes to suck nitrogen gas from the other side, as shown in FIG. 14 (plan view).
Example 5
[0074] This example demonstrates a semiconductor device of SOI (silicon on insulator) structure which is produced as follows. A silicon substrate is coated with a thermal oxide film, 0.5 μm thick, on which is subsequently formed an amorphous silicon film, 50 nm thick, by CVD process. The amorphous silicon film is annealed by laser beam scanning (with two-shot overlapping) through a phase-shifting mask placed 0.6 mm away from the substrate. This mask has a stripy pattern scribed at a pitch of 2 μm. The foregoing steps are followed by the ordinary procedure to form transistors on the polysilicon layer resulting from annealing. Thus there is obtained the desired SOI device. Incidentally, the thermal oxide film mentioned above may be replaced by an oxide film formed by CVD process. The thickness of the oxide film is not restricted to 0.5 μm.
Example 6
[0075] This example demonstrates annealing by scanning with CW laser through a phase-shifting mask having a periodic stripy pattern. The CW laser used in this example is YAG laser (10 W) having a wavelength of 532 nm as the second harmonics. Scanning is accomplished with a linear beam (500 μm in long axis and 10 μm in short axis) shaped by two cylindrical lenses of different type. The phase-shifting mask has a stripy pattern scribed at a pitch of 10 μm. The stripy pattern is inclined 35 degrees with respect to the scanning direction. This angle meets the requirements specified in FIG. 16 . Scanning as mentioned above gives rise to a polycrystalline silicon film in which crystals grow in the lateral direction. The thus obtained polycrystalline silicon film is free from hillocks running parallel to the direction of stripes, unlike the one obtained by irradiation with pulsed laser beams.
[0076] As mentioned above, the present invention provides an improved process for laser annealing which makes it possible to produce a high-quality crystalline silicon thin film, which cannot be obtained by simply repeating laser irradiation, more efficiently than the conventional process.
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To improve the laser annealing process for polycrystallizing amorphous silicon to form silicon thin films having large crystal particle diameters at a high throughput, the present invention is directed to a process of crystallization by irradiation of a semiconductor thin film formed on a substrate with pulsed laser light. The process comprises having a means to shape laser light into a linear beam and a means to periodically and spatially modulate the intensity of pulsed laser in the direction of the long axis of the linear beam by passing through a phase-shifting stripy pattern perpendicular to the long axis, and collectively forming for each shot a polycrystalline film composed of crystals which have grown in a certain direction over the entire region irradiated with the linear beam.
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BACKGROUND
The present invention relates to a method of power management in an electrically-assisted vehicle such as an electrically-assisted bicycle. It will be within the abilities of those skilled in the art to adapt the provided method to other types of electrically-assisted vehicles, for example, a electrically-assisted scooter, an electrically-assisted oar, etc. More generally, in the present application, electrically-assisted vehicle designates any vehicle intended to be driven by human force, and provided with a motor-driven electrically assistance capable of completing human power or of occasionally replacing it.
DISCUSSION OF THE RELATED ART
FIG. 1 very schematically shows an electrically-assisted bicycle 1 . Such a bicycle comprises a crank gear 3 , connected to the back wheel hub via a chain and toothed wheels (not shown). Bicycle 1 further comprises a pedal-assist motor 5 , electrically powered by a battery 7 . Motor 5 is arranged so that, in operation, it rotates the back hub to relieve the cyclist's effort. There exist variations where the assistance motor can be arranged to drive the crank gear, the front hub, or the actual wheel, for example, via a friction roller. In the shown example, battery 7 is located at the level of the back luggage carrier of the bicycle.
Bicycle 1 comprises a control unit 9 enabling the user to control the starting of motor 5 . Unit 9 for example enables to choose from among a plurality of assistance levels (low, medium, high, etc.).
Control unit 9 also comprises an indicator of the battery charge state. It may be a display directly displaying the total quantity of electric power available in the battery, in the form of a numerical value (for example, in ampere hours) or in the form of a graphic representation. The display may also display in real time the electric power consumed by the motor (for example, in watts) and various pieces of information such as the speed, the number of kilometers traveled, etc.
In certain systems, unit 9 displays an estimate of the number of kilometers that the user can still travel before the battery reaches a critical discharge level. It however is a rough estimate, calculated, for a given assistance level, by only taking into account the battery charge state.
A disadvantage of current control systems is that they do no enable to provide an accurate indication of the bicycle range.
Another disadvantage of current control systems is that they do not enable the user to intelligently manage the use of the power assistance during an itinerary.
SUMMARY
An object of an embodiment of the present invention is to provide a method of power management in an electrically-assisted vehicle such as an electric bicycle, at least partly overcoming some of the disadvantages of current solutions.
An object of an embodiment of the present invention is to provide a power management method enabling to determine the vehicle range with more accuracy than current solutions.
An object of an embodiment of the present invention is to provide a power management method enabling the user to easily choose an itinerary according to the quantity of electric power available in the battery.
An object of an embodiment of the present invention is to provide a power management method enabling the user to better manage his effort during an itinerary, by taking into account the quantity of electric power available in the battery.
Thus, an embodiment of the present invention provides a method of power management in an electrically-assisted vehicle, this method being implemented by an on-board computer provided in the vehicle, comprising the steps of: a) dividing into elementary sections an itinerary between a starting point and an arrival point; b) for each elementary section, determining the total amount of power necessary to travel the section, assigning an amount of human power to the section, and deducing therefrom the amount of electric power necessary to travel the section; and c) deducing the last elementary section that the vehicle can travel from the starting point before a battery of the vehicle reaches a threshold.
According to an embodiment of the present invention, steps a) and c) are repeated for a plurality of different itineraries having a same starting point.
According to an embodiment of the present invention, the power management method further comprises a step of displaying in the form of a cartographic representation a plurality of points that the user is capable of reaching before the battery reaches the threshold.
According to an embodiment of the present invention, the total amount of power necessary to travel a section is determined by taking into account prerecorded topographic data specific to the section.
According to an embodiment of the present invention, the power management method comprises a step of measuring the average power delivered by the user.
According to an embodiment of the present invention, the power management method comprises a step of geolocation of the vehicle.
According to an embodiment of the present invention, the power management method comprises a step of measuring the total amount of power available in a battery of the vehicle.
Another embodiment of the present invention provides a power management system in an electrically-assisted cycle, comprising an on-board computer capable of: dividing into elementary sections an itinerary between a starting point and an arrival point; for each elementary section, determining the total amount of power necessary to travel the section, assigning an amount of human power to the section, and deducing therefrom the amount of electric power necessary to travel the section; and deducing the last elementary section that the vehicle can travel from the starting point before a battery of the vehicle reaches a threshold.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features and advantages will be discussed in detail in the following non-limiting description of specific embodiments in connection with the accompanying drawings, among which:
FIG. 1 , previously described, schematically shows an example of electrically-assisted bicycle;
FIG. 2 is a timing diagram showing steps of an embodiment of a method of power management in an electrically-assisted vehicle, enabling to manage the use of the assistance along an itinerary;
FIG. 3 illustrates an example of display of data determined by the method described in relation with FIG. 2 ;
FIG. 4 is a flowchart showing steps of an embodiment of a method of power management in an electrically-assisted bicycle, enabling the user to choose an itinerary according to the amount of electric power available in the battery; and
FIG. 5 illustrates an example of display of data determined by the method described in relation with FIG. 4 ; and
FIG. 6 is a block diagram showing in simplified fashion an embodiment of a system of power management in an electrically-assisted bicycle.
DETAILED DESCRIPTION
To help the user manage the use of the electric power in an electrically-assisted vehicle such as an electrically-assisted bicycle, a method comprising a step of determining the total amount of power necessary to travel a section is here provided. Knowing the total amount of power necessary to travel the section, an amount of electric power is assigned to the section and the effort, that is, the amount of human power to be provided by the user to travel the section, is deduced therefrom. In an alternative embodiment of the provided method, an amount of electric power is assigned to the section and, knowing the average power delivered by the user, it is deduced whether the vehicle can or not travel the entire section.
FIG. 2 is a flowchart showing steps of an embodiment of a method of power management in an electrically-assisted bicycle. In this example, the method is at least partially implemented by a management system such as an on-board computer or an equivalent system comprising at least one calculation unit. The on-board computer is associated with a navigation system and can access cartographic databases. The navigation system is preferably associated with geolocation means, for example, a GPS (“Global Positioning System”). The navigation system may further access prerecorded topographic data, for example, a topographic database, so that, for a given itinerary, the on-board computer can determine in advance the topographic profile of the itinerary.
During a step 21 (“location”), the starting point of an itinerary to be traveled is determined. The starting point may correspond to the current position of the bicycle, automatically determined by the geolocation means. In an alternative embodiment, the user may himself input the coordinates of the starting point of the itinerary.
During a step 22 (“input destination”), the user inputs the coordinates of a destination, or arrival point of the itinerary to be traveled.
During a step 23 (“battery power measurement”), the management system measures the amount of electric power available in the battery, for example, by means of a gauge connected both to the battery and to the on-board computer.
During a step 24 (“topography acquisition”), the system acquires the topographic data corresponding to the itinerary determined at steps 21 and 22 , and deduces therefrom the topographic profile of the itinerary, that is, the elevation as a function of distance. Topographic maps may be pre-recorded in the on-board computer. In another embodiment, the on-board computer may access a distant server containing cartographic and/or topographic data by means of wireless communication means, for example, of GSM type.
During a step 25 (“electric power distribution”), the total amount of power (electric+human) necessary to travel the itinerary is determined, and the amount of available electric power is distributed and assigned to different portions of the itinerary.
In a preferred embodiment, the itinerary is divided into elementary sections or routes. For each section, the total power required to travel the section is determined, taking into account the topographic profile of the section. Other parameters may be taken into account, such as the average displacement speed desired over the section and the bicycle weight, including the cyclist, or also the wind speed and the tire pressure, by means of appropriate sensors enabling, in particular, to estimate the different components opposing the bicycle motion.
The amount of power available in the battery is then distributed between the different sections. Each section is assigned an amount of electric power selected so that the user can travel the entire itinerary without for the battery to reach a critical discharge level or threshold. As an example, if the vehicle is provided with a system for recharging the battery in downhill slopes, the electric power distribution method takes it into account. Thus, if the itinerary comprises downhill sections, a greater part of the available electric power is assigned to the sections preceding the downhill sections, since it is known that the battery will at least partially recharge during downhill slopes. More generally, it is provided to distribute the available electric power to minimize and to better distribute the user's effort while ascertaining that he reaches his destination with still a minimum battery charge level. Of course, according to the itinerary, and possibly of a usage mode selected by the user (city, leisure, sports, etc.), it may be provided not to consume the entire available electric power, and thus to adjust the electric assistance level. As a variation, if the electric battery appears not to contain enough power to travel the entire itinerary, it may be provided to decrease the assistance level on certain less demanding sections and to require an additional human power contribution from the user. In an embodiment, the user may select a desired average speed over the itinerary. The electric power may then be distributed to respect at best the desired speed all along the itinerary.
Knowing the total amount of power necessary to travel each section, and having assigned to each section an amount of electric power, the system deduces the amount of human power to be delivered by the user to travel each section.
It should be noted that one of the criteria of distribution of the electric power at step 25 may precisely be to make the effort requested from the user as uniform as possible all along the itinerary. Any other electric power distribution criterion may be selected.
During a step 26 (“display”), the on-board computer indicates to the user, for each section of the itinerary, the amount of power or the average power that he should deliver to travel the section. Optionally, a feedback control of the electric power-assist motor may be provided to automatically control the assistance level according to the amount of electric power assigned to each section at step 25 . This enables for the user to envisage no other manipulation than inputting his destination coordinates.
FIG. 3 illustrates, as an example, a mode of display, for the user, of data determined by the method described in relation with FIG. 2 . A display screen of the on-board computer displays topographic profile P of the itinerary, that is, elevation h as a function of distance d, between starting point D and arrival point A of the itinerary. Profile P is divided into sections, and for each section, the human power that the cyclist will have to deliver to travel the section is indicated. In this example, the average power is indicated in watts. The invention is of course not limited to this specific display mode. Any other form of display may be provided.
Further, it may be provided to recalculate the electric power distribution at one or a plurality of intermediate points of the itinerary. This enables to readjust the calculation in the case where, on the sections already traveled, the cyclist would have delivered more or less than the initially-determined recommended average effort.
An advantage of the provided method is that it enables to manage the use of the electric power assistance along an itinerary selected by the user.
It should in particular be noted that the use of prerecorded topographic data enables to anticipate the elevation data over the complete travel, and thus to anticipate the power consumption over the travel.
FIG. 4 is a flowchart showing steps of another embodiment of a method of power management in an electrically-assisted bicycle.
During a step 41 (“location”), the cyclist's starting point is determined. The starting point for example corresponds to the current position of the vehicle, and may be automatically determined by geolocation means. As a variation, the user may himself input the coordinates of the starting point.
At a step 42 (“battery power measurement”), the management system measures the quantity of electric power available in the battery, for example, by means of a gauge connected to the on-board computer.
At a step 43 (“cyclist power acquisition”), the average power delivered by the cyclist (human power) is determined. In a simplified embodiment, it may be a value pre-recorded in the on-board computer. A system comprising a plurality of usage modes (city, leisure, sports, etc.) may for example be provided, each usage mode corresponding to a value of the average power delivered by the cyclist. In a preferred embodiment, the average delivered power is measured in situ by means of adapted sensors provided on the bicycle.
At a step 44 (“topography acquisition”), the system acquires the cartographic and topographic data of a geographic area having as a center the starting point determined at step 41 .
At a step 45 (“calculation of possible destinations”), the on-board computer calculates, taking into account the average power delivered by the cyclist as well as the available electric power and the topography, the maximum distance that the bicycle can travel (or bicycle range), in one or a plurality of directions from the starting point determined at step 41 . In an embodiment, an angular scanning of the map is performed, from the starting point determined at step 41 . The vehicle range is calculated for all the successive scanning directions. As an example, an angular resolution between 1 and 10 degrees may be selected. This enables to specifically indicate to the user his radius of action, that is, all the points that he can reach without for the battery to reach a critical discharge level.
In an embodiment, for each angular scanning direction, the point determined at step 41 is selected as the starting point of an itinerary. A point sufficiently distant from the starting point and belonging to the considered angular direction is selected as the arrival point of the itinerary. “Sufficiently distant” means that the distance between the starting point and the arrival point is greater than the maximum range of the bicycle in favorable conditions. For example, the arrival point may be selected at a distance from the starting point 1.5 greater than the theoretical range of the bicycle on level ground, with a charged battery.
The itinerary thus determined is divided into sections or elementary sections. For each section, the total power required to travel the section is determined, taking into account the prerecorded topographic data. Other parameters may be taken into account, such as the average displacement speed over the section and the bicycle weight, or also the air resistance (for example, estimated by measuring the wind speed) or the rolling resistance (for example estimated by measuring the tire pressure). The amount of human power delivered by the cyclist on each section is calculated, taking into account the cyclist's average power determined at step 43 . Thus, each section is assigned a given amount of human power. Knowing the total amount of power necessary to travel each section, and the amount of human power assigned to each section, the system determines the amount of electric power necessary to travel each section. The last section of the itinerary that can be traveled from the starting point before the battery reaches a critical discharge level is then determined.
Any other adapted method may be used to determine the most distant point that the cyclist can reach in a given direction.
In an alternative embodiment, to determine the possible destinations, the cartographic data are used to only consider destinations and itineraries located on roads or tracks where a bicycle can be ridden.
At a step 46 (“display”), the on-board computer indicates to the user, for each direction of the angular scanning performed at step 45 , the vehicle range. This information is for example displayed on a geographic map, in the form of a curve showing all the destinations accessible from the starting point determined at step 41 .
FIG. 5 illustrates, as an example, a mode of display, for the user, of data determined by the method described in relation with FIG. 4 . A display screen of the on-board computer displays map 51 of a geographic area having as a center starting point D determined at step 41 . A curve C showing all the destinations accessible from starting point D is overlaid on map 51 . Any other form of display may of course be provided. It may in particular be provided to display a plurality of curves, corresponding to a plurality of assistance levels (sports, city, leisure, etc.) and/or of average power delivered by the cyclist. It may further be provided to recalculate the possible destinations on the way, to readjust curve C in the case where the cyclist would have delivered more or less than the effort corresponding to the average power determined at step 43 .
An advantage of this embodiment is that it enables to more accurately and more realistically determine the vehicle range than current solutions. Further, the provided power management method enables the user to easily select an itinerary, taking into account the real range of the vehicle over this itinerary.
FIG. 6 is a block diagram showing in simplified fashion an embodiment of a system of power management in an electrically-assisted bicycle.
The management system comprises a calculation unit 60 (μP), for example corresponding to a on-board computer microprocessor. A sensor 62 (P cycl ) capable of measuring the power delivered by the cyclist is connected to calculation unit 60 . A sensor 61 (E bat ) capable of determining the amount of electric power available in the battery is connected to calculation unit 60 . Calculation unit 60 is further connected to a topographic and/or cartographic data base 63 (Topo). Database 63 may be local, that is, recorded in a memory of the on-board computer. As a variation, database 63 may be recorded by a distant server to which the on-board computer can access by wireless communication means, for example, via a GSM-type network. In this example, a geolocation module 64 (GPS) is connected to calculation unit 60 . Further, a display 65 (Display) is provided, to display data for the user.
Specific embodiments of the present invention have been described. Various alterations, modifications, and improvements will readily occur to those skilled in the art.
In particular, the invention is not limited to the above-described examples where the total power necessary to travel a section is determined by taking into account the real topography of the section. Simpler embodiments may be provided, where the total power necessary to travel a section is determined by taking into account the length of the section and, possibly, a standard average elevation (pre-recorded) corresponding to a usage mode selected by the user (flat ground, hills, mountain, etc.).
Further, the provided power management method has been more specifically described in relation with an example of use in an electrically-assisted bicycle. The present invention is not limited to this specific example.
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A method for energy management in an electrically assisted vehicle includes the steps of determining the quantity of total energy required for a journey and allocating a quantity of electrical energy to the journey and deducing the quantity of human energy required for the journey on the basic thereof, or allocating a quantity of human energy to the journey and deducing the quantity of electrical energy required for the journey on the basis thereof.
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TECHNICAL FIELD
This invention relates to a work machine, such as an excavator, backhoe, front shovel or material handler, more particularly to the structure of a stick and/or boom for use with the work machine.
BACKGROUND
In a typical arrangement, the boom and stick have an enclosed, box like configuration. For example, U.S. Pat. No. 3,220,578 discloses a stick having an enclosed, box-like shape.
Structural members for work machines such as backhoes, excavators and front shovels typically include a boom pivotally attached to a machine frame at a first end, a stick pivotally attached to the boom at a second end and a bucket or material handling device further attached to the stick. Drive mechanisms, often hydraulic cylinders, are coupled to the machine in manner that moves the boom relative to the machine frame, the stick relative to the boom and the material handler relative to the stick.
In order to achieve the desired movement of structural members, sticks and booms are typically have three pivot (attachment) points. Two of the three pivot points are typically disposed at the first and second end, respectively, of the boom or stick. The first and second pivot points typically define a first longitudinal axis. The third pivot point is typically disposed at a predetermined distance from the first longitudinal axis. A second axis can be defined by extending a line from the first pivot point to the offset pivot point and a third axis can be defined by extending a line from the second pivot point to the offset pivot point. The first longitudinal axis, the second axis and the third axis form a triangle.
A problem with the box-like configuration is that such a structure is high in cost to manufacture and heavy in weight. When the boom or stick is unnecessarily heavy, the amount of material such as dirt or rock that can be carried by a bucket is reduced, thus requiring extra bucket loads to fill a truck. The additional weight also induces additional stress into other components of the work machine; this may adversely effect the life of the work machine. The power requirements to lift or move the additional weight increases the engine and related component size, resulting in increased machine cost. Unnecessary weight, generally, reduces efficiency and increases operating costs of the machine.
The present invention is directed toward overcoming one or more of the problems set forth above.
SUMMARY OF THE INVENTION
In an embodiment of the present invention, a work machine having at least one of a boom and a stick. A material-handling device is attached to the boom or stick. The boom or stick being constructed of a box portion and an attached truss portion.
In another embodiment of the present invention, a structural member for a work machine is disclosed. The structural member has a first end and a second end, a first pivot point disposed adjacent the first end and a second pivot point is disposed adjacent the second end. The structural member comprises an offset pivot point having a plurality of longitudinal members extending to the box section, forming a rigid structure.
In yet another embodiment of the present invention, a method of reducing the weight in one of a stick and boom of a work machine. The method includes constructing a box portion having a first pivot point, a second pivot point and a first longitudinal axis extending therethrough. A truss portion is constructed having a plurality of longitudinal members intersecting a third pivot point. Attaching the truss section to the box section completes the stick or boom.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a portion of a work machine, according to one aspect of the present invention.
FIG. 2 is a side view of a boom of a work machine, according to another aspect of the present invention.
DETAILED DESCRIPTION
Referring to FIG. 1, a work machine 10 includes a boom 12 , a stick 14 and a material-handling device 16 . In this application an excavator is used to define the work machine 10 , the material handling device 16 is a bucket 18 . However, the invention may be applied to other types of work machines, such as a wheel loader, backhoe, or telescopic material handler. In the case of a wheel loader, one material-handling device could have a mechanism for grasping the material, such as a grapple. The stick 14 is pivotally connected to the boom 12 at stick pivot point 20 and the bucket 18 is pivotally connected the stick 14 at bucket pivot point 22 .
According to one aspect of the present invention, the stick 14 includes a first portion (box portion) 24 that is constructed from a plurality of plate sections attached to one another to create a box or rectangular cross-section. The box portion 24 is substantially enclosed around its periphery, as illustrated in FIG. 1 . According to this embodiment, the truss portion 26 includes a pair of triangular truss members 28 that are spaced apart from each other and interconnected by cross members 30 . The truss portion 26 is pivotally connected to the box portion 24 at base pivot point 32 so that it is free to rotate with respect to the box portion 24 . More specifically, a base plate 34 is secured to the box portion 24 and the truss portion 26 is pivotally attached to the base plate 34 at base pivot point 32 . However, it is important that the truss portion 26 be generally fixed in relation to the box portion 24 . Therefore, a pair of support members 36 extend from the end of the truss portion 26 to the box portion 24 to prevent the truss portion 26 from rotating with respect to the box portion 24 about pivot point 32 . As a result of this arrangement, the truss portion 26 is able to withstand forces created during operation of the machine. However, it should be understood that the invention is not limited to having the truss portion 26 pivotally secured to the base plate 34 . One suitable alternative would be to have the truss portion 26 solidly attached (e.g., integrally attached) to the box portion 24 . Another alternative is to mount the truss portion 26 using the current stick 14 to boom 12 connecting pin 20 .
It should be noted that the base plate 34 may either be integrally secured to the box portion 24 or, alternatively, the base plate 34 may be removably attached using bolts, screws, or the like. Further, it should be understood that this is just one example of a suitable truss portion 26 and the invention is not limited to any particular truss design.
A first drive mechanism 38 is provided for pivoting the stick 14 with respect to the boom 12 . A second drive mechanism 40 is provided for pivoting the bucket 18 or material handling device 16 with respect to the stick 14 . A third drive mechanism (not shown) is provided for pivoting the boom 12 with respect to a machine frame. In this application, a typical drive mechanism includes a hydraulic cylinder 44 and rod 46 . A number of drive mechanisms may be used in place of the cylinder 44 and rod 46 , including cables and pulleys.
With respect to the first drive mechanism 38 , the base end of the cylinder 44 is pivotally connected to the boom 12 at pivot point 48 and distal end of the rod 46 is pivotally attached to the truss portion 26 at a first truss pivot point 50 . With respect to the second drive mechanism 40 , a base end 52 of the cylinder 44 is pivotally connected to the truss portion 26 at a second truss pivot 54 and the distal end of the rod 46 is pivotally connected to a linkage 56 at a linkage pivot point 58 . The linkage 56 includes a first pair of link members 60 which are pivotally connected at one end to the distal end of the rod 46 at the first linkage pivot point 58 and at the other end to the stick 14 at a second linkage pivot point 62 . The linkage further includes a second pair of link members 64 which are connected at one end to the first linkage pivot point 58 and at the opposite end to a back of the bucket 18 at a third linkage pivot point 66 . The linkage and drive mechanisms are conventional and the invention is not intended to be limited to any particular linkage or drive mechanism.
According to another aspect of the invention, the boom 12 ′ may included a truss portion 26 ′ in combination with a box portion 24 ′. More specifically and with reference to FIG. 2, the boom 12 ′ may include the first portion (box portion) 24 ′ and the second portion (truss portion) 26 ′. The truss portion 26 ′ includes a first pair of truss members 70 , 72 which, together with the box portion 24 ′ forms a triangle. Although not shown, a second pair of truss members may be laterally spaced from the first pair of truss members 70 , 72 , and suitably interconnected by one or more connecting members, as with the truss portion 22 discussed in regard to the stick 14 .
The boom 12 ′ is pivotally attached to the machine 10 and the stick 14 ′ is pivotally attached to the boom 12 ′. More specifically, a first end 74 of the boom 12 includes a boom pivot point 76 for pivotally attaching the boom 12 to a machine frame 78 . Correspondingly, a second end 80 of the boom 12 includes the stick pivot point 18 ′ for pivotally attaching the stick 14 to the boom 12 . The truss portion 16 ′ includes the pivot point 48 ′ for attaching the first drive mechanism 36 ′. The first drive mechanism 36 ′ further attaches to a stick.
Industrial Applicability
In operation, the apparatus of the present invention operates in a conventional manner. For example, the first drive mechanism 38 is operable to pivot to stick 14 with respect to the boom 12 . The second drive mechanism 40 is operable to pivot the bucket 18 or material handling device 16 with respect to the stick 14 and the third drive mechanism 42 is operable to pivot the boom with respect to the machine frame (not shown).
The present invention provides a stick 14 and boom 12 that is constructed with less steel, therefore reducing the weight and cost of the structure. The reduced structure weight additionally increases the amount of material that the bucket 18 can lift. Fuel efficiency is also improved due to the reduced weight, because the machine is not required to move the excess weight. In some cases, the amount of weight reduction of the structure may increase payload capacity enough to reduce the horsepower requirement for the engine, allowing the use of a lower cost engine. In other cases the increase payload capacity may permit use of a smaller machine, saving the customer some capital expense.
In addition, it is possible to have a variety of truss designs adapted to fit different machine configurations. A single machine may be reconfigured for different functions by changing the material handling device 20 , the stick 14 or the boom 16 .
It should be understood that while one embodiment is described in connection with an excavator, the present invention if readily adapted to provide similar functions for other work machines. Other aspects, objects and advantages of the present invention can be obtained from a study of the drawings, the disclosure and the appended claims.
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A stick or boom for a work machine. The stick or boom has a box portion including a first and second end and a first and second pivot point position at respective ends. A truss portion having an offset pivot point is attached to said stick or boom.
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This invention relates to an improved method for the preservation of the freshness of seafood. More particularly, this invention relates to an improved method for the preservation of shrimp using a blend of bisulfite and sulfite as the preservative.
BACKGROUND OF THE INVENTION
Fresh seafood has a limited shelf life before it spoils. The shelf life of some seafoods can be extended by cold storage and the like, but some seafood, particularly shrimp, has a shelf life of only a few days even when packed in ice.
Thus various treatments have been suggested to extend the shelf life of foods, particularly seafood.
Melanosis, or black spot, is an ailment that afflicts shrimp and results in the appearance of black spots, which is an indication of loss of freshness to the consumer. Shrimp, for example, darken and develop dark spots as they age. Thus shrimp can be examined visually to determine the degree of freshness. The test results for melanosis range from 0, that is, no spoilage, to 10, indicating extreme spoilage.
The usual treatment to reduce melanosis in shrimp is to treat the fresh shrimp with a dilute solution of sodium metabisulfite (Na 2 S 2 O 5 ) which forms sodium bisulfite (NaHSO 3 ) in solution. The usual application is by immersing the shrimp in a dilute (1.25% by weight) sodium metabisulfite solution for one minute. This treatment retards the spoilage of fresh shrimp, and the use of this treatment has become standard practice for shrimp just after the shrimp are harvested. Thus ocean harvested shrimp are treated on the shrimp boats as soon as they are harvested, and they may be treated again during the preparation and packaging steps prior to shipment.
Shrimp grown by aquaculture generally are harvested at night, treated with sodium metabisulfite solution in the field, iced, and taken to the processing plant. Here they are iced again, re-treated with sodium metabisulfite solution, cleaned, graded as to size, packed in paper cartons and quick-frozen. So great is the concern with freshness that the time from harvesting to freezing is usually no more than twelve hours.
Although effective to retard spoilage, a dilute, i.e., 1.25% by weight sodium metabisulfite solution, produces a noticeable and objectionable odor of sulfur dioxide. While this amount of sulfur dioxide is generally considered safe, nevertheless it can be irritating to workers in closed environments, such as in the hold of a ship where the chemical is being used, and to workers during processing of the shrimp that have been treated with the sodium metabisulfite. For persons who are allergic to sulfur dioxide, such as asthmatics, its presence may be dangerous. The odor of sulfur dioxide may even be detected by consumers, who object to it.
The use of sodium metabisulfite as a shrimp preservative has continued however, because it is very effective. However, good ventilation equipment must be provided when sodium metabisulfite is being used.
Thus the provision of an effective, safe and inexpensive substitute for sodium metabisulfite solutions to preserve the freshness life of seafood, particularly shrimp, while substantially reducing the odor, i.e., practically eliminating the odor, of sulfur dioxide, would be highly advantageous.
SUMMARY OF THE INVENTION
I have found that particular mixtures of sodium metabisulfite that include sodium sulfite are very effective for preserving the freshness of seafood, and shrimp in particular. The advantages of mixtures of the invention which employs sodium sulfite over sodium metabisulfite alone as a preservative are considerable. The mixtures of the invention produce a greatly reduced odor of sulfur dioxide. Thus the present invention is directed to treating seafood with a solution comprising sodium metabisulfite mixed with from about 30% up to 50%, and more suitably 35 to 45% of sodium sulfite. The preferred proportion is about 40% of the sodium sulfite. Aqueous solutions of these mixtures are safer to use than sodium metabisulfite alone in that they produce insignificant, or minimal sulfur dioxide odor, but they are substantially and practically as effective for preserving seafoods, particularly shrimp, without the extremely objectionable odor of sulfur dioxide that is present when using the sodium metabisulfite alone.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a graph of pH versus concentration for sodium metabisulfite compared to a mixture of sodium metabisulfite and sodium sulfite of the invention.
FIG. 2 is a graph showing the effect of pH on vapor pressure of sulfur dioxide over sodium metabisulfite solutions.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the method of the invention, a solution of at least 0.5% by weight and up to about 3% by weight of a mixture of sodium metabisulfite and sodium sulfite is applied to shrimp and other seafood. The solutions are applied by any suitable means that substantially saturates the shrimp with the sodium metabisulfite-sodium sulfite solution, such as by applying to the shrimp a thorough spraying or mist of the solution, or by immersing the seafood in the solution or by conveying it in mechanical fashion through the solution. The solutions can have a higher concentration, provided that the treated product has a residual content of less than about 100 ppm of sulfur dioxide, and preferably less than 80 ppm, in order to comply with various governmental guidelines.
The reason for the high sulfur dioxide generation in sodium metabisulfite solutions can be explained by referring to FIGS. 1 and 2. FIG. 1 is a graph of pH versus concentration for sodium metabisulfite, line A, and a 60:40% by weight mixture of sodium metabisulfite and sodium sulfite, line B. Sodium metabisulfite has a low pH that decreases with its concentration; it is always at an acid pH, below about pH 4.5. This increases its vapor pressure as shown in FIG. 2. From FIG. 2 it is apparent that at a lower pH, the vapor pressure of sulfur dioxide metabisulfite solution is high, whereas at a higher pH of about 5.5-6.0, the vapor pressure of sulfur dioxide over the solution decreases rapidly. Thus the more acidic solution readily forms sulfur dioxide gas which volatilizes from the solution. This is borne out by experience. A 2% by weight solution of sodium metabisulfite in water has a strong odor of sulfur dioxide.
A mixture of sodium metabisulfite and sodium sulfite however, has a much higher pH, above 5.9 at any concentration: up to the solubility limit, and thus the volatilization of SO 2 is reduced. A 2% by weight solution of this mixture in water has no significant odor of sulfur dioxide.
The invention will be further described and tested with respect to shrimp, but it is to be understood that the present method can be used for other seafood, such as other shellfish.
In order to measure the spoilage of shrimp over time, the shrimp, either fresh or defrosted, were immersed in various aqueous solutions containing sulfites, using water as a control, for 1.0 minute. The shrimp were then packed in ice and examined every other day for a period of two weeks. The shrimp were graded for melanosis.
The following Table I illustrates the ratings, i.e., the degree of melanosis and descriptions for melanosis employed herein:
TABLE I______________________________________Rating Description______________________________________0 Absent2 Slight, noticeable on some shrimp4 Slight, noticeable on most shrimp6 Moderate, noticeable on most shrimp8 Heavy, noticeable on most shrimp10 Heavy, totally unacceptable______________________________________
Table II below summarizes melanosis data for shrimp dipped in various solutions in a concentration of 1.0% by weight over time. Solution 1 was a 100% by weight of sodium metabisulfite solution; solutions 2 to 5 contained both sodium metabisulfite and sodium sulfite in the proportions shown. Solution 6 was 100% by weight of sodium sulfite solution. The Control was water. The data is presented as an average of three test results for the indicated elapsed number of days after treatment.
TABLE II______________________________________ Melanosis Rating, Elapsed DaysSolution 1 3 5 7 9 11 13______________________________________1 (100:0) 0 0 2.3 4 5.7 7.3 8.72 (85:15) 0 0 3.3 5.3 6.3 8.0 8.73 (60:40) 0 0.7 3.0 5.0 6.0 8.3 8.74 (35:65) 0 1.0 5.3 7.7 7.7 9.0 10.05 (12.5:87.5) 0 2.0 5.7 6.3 6.7 8.0 9.36 (0:100) 0 2.7 5.3 7.3 7.7 9.3 9.3Control 1.7 4.3 6.7 8.7 9.0 9.7 10.0______________________________________
Thus all of the sulfite-containing solutions reduced melanosis compared to the Control, and the solution of 100% sodium metabisulfite was the most effective. However, mixing up to about 40% of sodium sulfite with the sodium metabisulfite had very little negative effect on melanosis, but a dramatic effect on the residual odor of sulfur dioxide.
Increasing the concentration of the mixed sulfite solutions to 2.0% by weight did show some positive results, as shown below in Table III.
TABLE III______________________________________ Melanosis Rating, Elapsed DaysSolution 1 3 5 7 9 11 13______________________________________1 (100:0) 0 0 0 7 3.3 4.3 5.72 (85:15) 0 0 1.0 2.7 4.0 5.3 7.03 (60:40) 0 0 0.7 3.0 3.7 5.0 6.34 (35:65) 0 0 1.7 4.0 5.3 6.3 7.05 (12.5:87.5) 0 0 1.7 3.3 5.0 6.7 7.36 (0:100) 0 0 2.3 5.0 6.3 7.7 8.3Control 0 3.3 6.7 8.7 8.7 9.7 10.0______________________________________
It is apparent that some benefits are seen for sodium metabisulfite alone or in combination with minor amounts (less than 50%) of sodium sulfite. The melanosis ratings for up to 60:40 solutions remained below 7 after 13 days.
However, less concentrated solutions were less effective. 0.5% solutions did not prevent melanosis for longer than one week for any of the solutions.
The sulfite residuals in ppm on the shrimp treated with solutions of various concentration were also determined. The data is given below in Table IV as an average of three determinations.
TABLE IV______________________________________ RESIDUAL SULFUR DIOXIDE, PPMSolution 0.5% 1.0% 2.0%______________________________________1 (100:0) 22.18 42.53 88.672 (85:15) 31.39 34.50 67.333 (60:40) 15.48 18.77 60.204 (35:65) 28.61 44.51 25.575 (12.5:87.5) 18.88 48.49 84.676 (0:100) 12.53 48.49 84.67______________________________________
It is apparent that none of the solutions reached the limit of 100 ppm. The residual sulfite concentration is lowest for a 1.0% solution of 60% sodium metabisulfite and 40% sodium sulfite. Coupled with the highly effective treatment with this solution for increasing shrimp shelf life, such solutions are both highly effective and greatly reduce the generation of SO 2 .
The concentration of sodium metabisulfite and sodium sulfite used for treating foods can be varied, providing the residual sulfur dioxide equivalent in the food is below acceptable maximums. Increasing the concentration of the treating solution will prolong shelf life without increasing the odor of sulfur dioxide, but may increase the amount of residual sulfite remaining on the food.
Although the invention has been described in terms of specific tests and embodiments, one skilled in the art can substitute other tests and embodiments and these are meant to be included herein. The invention is only to be limited by the scope of the appended claims.
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Shrimp and other seafood can be preserved to extend their freshness shelf life by immersing them in an aqueous solution prepared by dissolving a dry mixture containing sodium metabisulfite with from 30 to 50% by weight of sodium sulfite. These solutions have excellent preservative action yet have very little or no odor of sulfur dioxide. The solutions are useful in a concentration of up to about 3% by weight.
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BACKGROUND
1. Field of Invention
This invention relates to protective devices for windows, specifically a reusable multiple-panel, foldable security device and method for protecting double-hung windows with the perimeter edges of the device fitting within the outermost groove of a double-hung window frame and having a plurality of opposing straps attached thereto which are drawn rearward both over and under the double-hung window sashes during installation. The opposing straps connect taut behind the closed and locked double-hung window sashes to secure the protective panels in place so that the security device cannot be easily removed by someone attempting to do so from the outside of the building. The aesthetically pleasing device is made from lightweight materials and in most instances can be easily installed and removed by one adult of average strength and coordination standing behind the double-hung window without the use of a ladder or tools. Also, installation of the security device of the present invention does not damage or cause permanent alteration of the double-hung window frame or the building surfaces adjacent to the window. Applications can include, but are not limited to, protecting a double-hung window from hazards such as storm debris, vandalism, burglary, and unauthorized entry.
BACKGROUND
2. Description of Prior Art
People continually look for easy and affordable ways to protect their homes and families from hazards associated with adverse environmental conditions, vandalism, and household entry by unauthorized persons. The windows of a house are likely to be the one part of a house most vulnerable to such hazards. High winds experienced during hurricanes, tornadoes, and typhoons can put houses and their windows at risk for damage from airborne debris. Historically, wooden shutters were pivotally mounted adjacent to building windows and closed as necessary over the window glass to protect it from storm damage, as well as secure the windows against unauthorized entry. However, while decorative shutters are still popular, functional shutters seem to be generally disfavored in modern architecture. Multiple-bladed rolling shutter systems, particularly those with automatic drive mechanisms, are an alternative to traditional wooden shutters and can be installed over windows as an effective way protect them against storm damage and intruders, however such shutter systems are expensive and usually require professional installation and maintenance.
Window protection needed against the hazard of storm debris requires a few considerations that are different from window protection used to avoid damage from vandalism and unauthorized entry. People in areas where tornadoes can be quickly spawned are usually given little or no advance warning of their arrival. As a result, any system protecting windows from tornado damage must be automatically engaged by a computer-aided home monitoring system at the first detection of increased wind velocity above a predetermined minimum velocity level, or if they are manually installed or engaged, window protection devices must already be positioned in front of the window sashes before any storm capable of producing tornadoes begins. One option would be to leave manually installed or manually engaged window protection devices in place during an entire spring or summer season in which one would expect enhanced tornado activity. However, homeowners would disfavor use of any window protection devices that detracted from the outward appearance of their homes, significantly blocked light entry into the home, or devices that blocked efficient egress from the home during emergencies.
In contrast, the arrival of hurricanes and typhoons are more accurately predicted than tornadoes and homeowners are usually given some time to prepare for their arrival. Therefore, the options used for window protection against hurricane and typhoon generated storm debris are more diverse. Homeowners who have installed window protection systems which require manual operation would have time to engage them. Other homeowners would have time to nail plywood over windows or place various types of adhesive-backed tape directly onto window glass. Installed systems are more expensive than the present invention and the use of plywood and tape both have significant disadvantages which are overcome by use of the present invention. For example, covering a window with plywood requires advanced planning, as it takes time to purchase the plywood, transport it to the needed site, measure it, cut it, and nail it into position. The present invention can be installed much faster. Also, installing plywood over a window requires tools and usually a ladder, particularly when upper story windows are involved. The present invention requires no tools and no ladder for an adult of average strength and coordination. Furthermore, plywood is heavy, and handling it may require more than one person, one person to hold large pieces of plywood in place over a window while a second person nails the wood to the window's frame or adjacent building surface. With the present invention, one adult of average strength and coordination can generally install it unless unusually windy conditions are present. Also, the installation of plywood over a window makes the window temporarily unusable. Aside from blocking entry of all light through a window, since plywood is installed against the outside of a building it is difficult to use the window as a means of egress during emergencies. The present invention can be made transparent or translucent to allow light to enter the building and its quick-release buckles that are easily accessible from the inside of the building allow for fast egress in emergencies. Furthermore, if not nailed skillfully, plywood can come loose during a storm whereby its protective capability becomes diminished or non-existent, and if it further becomes totally separated from the building it is likely to become a wind-borne projectile that could cause significant injury to other objects and people. The present invention has three design features which keep its protective panels securely in place, the panel edges fitting into the outermost groove in the outer frame of the double-hung window, the straps being held against the outer frame by the closed and locked upper and lower window sashes, and the straps which are connected taut behind the window sashes. Also, if the present invention were removed and allowed to fall to the ground during a storm for emergency egress through the window, its folding configuration and straps would reduce the likelihood of it becoming a wind-borne projectile. In addition, the installation of plywood over windows detracts from the aesthetic appearance of a house and as a result of being nailed directly to the outside of a building, it can be more readily removed by an intruder. The present invention does not detract from the appearance of a building and can have surface decorations on both its straps and panels which coordinate with the decor of a building. It is also made from shatter-resistant and impact-resistant materials and it cannot be readily removed by an intruder since the perimeter edges of its panels are inserted within the outermost groove of a double-hung window frame. The installation of plywood also places nail holes in a window's frame or adjacent building structure, and if plywood is repeatedly installed and removed from a building, the building will ultimately become damaged to the point that it will require repair. Installation of the present invention does not permanently alter window frames or any building surface adjacent to a window. Further, the use of plywood is not usually a cost effective means of window protection. Many homeowners only use it once or twice as they do not have adequate storage space for the bulky plywood pieces between storms or storm seasons. The present invention is easily reusable with minimal or no refurbishment between uses and it can be compactly folded for storage in a convenient location near to the window it is used to protect, such as under a bed or in a closet. The use of adhesive-backed tape directly on window panes also has disadvantages in that it is time consuming to install, it is messy to remove if the adhesive remains stuck on the glass surfaces during removal attempts, and it offers no significant protection against glass breakage. Since tape acts mainly to reduce glass dispersion upon breaking, it is likely that the window glass protected by adhesive-backed tape during hurricanes and typhoons would crack or break. Even if the glass is not dispersed, the interior of the building would still remain vulnerable to wind and rain related damage, as well as a target for vandals, particularly if the building was vacant when the window broke and a period of time elapsed prior to repair. The present invention is easy to install and remove, and it protects window sashes from breakage, as well as vandals and unauthorized entry.
The type of window protection needed to provide added security against vandals and intruders requires yet another set of considerations. Many homeowners use alarms and remote electronic monitoring systems for such purposes. While such systems are effective at reducing unauthorized entry into a house, both are expensive and do nothing to prevent the random acts of vandalism prevalent in some neighborhoods. A stray rock thrown through a window will set off an alarm which is likely to scare away a vandal, however, the window so damaged will still require a repair expense. Also, the broken window leaves the building vulnerable to storm damage, as well as a target of vandals and unauthorized entry prior to its repair. Some homeowners in particularly dangerous neighborhoods have chosen to use permanently installed window security bars to protect their homes from intruders. However, permanently installed window bars are expensive and sometimes cause fatalities during home fires when the barred windows prevent occupants from rapidly escaping.
Thus the reusable, lightweight, and transparent window covering of the present invention, which is both rapidly and easily installed and removed in most instances by one non-professional adult of ordinary strength and coordination but which resists removal by someone attempting to do so from the outside of the home and does not damage or permanently alter the window frame or building surfaces adjacent to the window, would provide a comprehensive solution for window protection from various environmental and criminal hazards. None of the window coverings currently available to homeowners provide all of the advantages of the present invention. While prior art window coverings do provide protection from environmental and criminal hazards, some are cumbersome to install and others require a variety of installation tools. Also, most must be installed and removed from the outside of the building and require the use of a ladder, particularly for upstairs windows. Further, while effectively protecting a window from outside hazards, some window coverings are less desirable than the present invention since they would not be easily removable during emergencies where a hasty exit through a window would be required. In addition, the present invention is simple to manufacture, it can be made from relatively inexpensive materials including recycled materials, it does not detract from the exterior appearance of the building when installed, it can comprise reinforcing bars for additional strength, its compact folded configuration makes it easy to store, and its straps allow it to remain securely in place during use while the quick-release strap fasteners simultaneously allow for quick egress through the window in emergencies.
The prior art thought to be most closely related to the present invention is the invention disclosed in U.S. Pat. No. 3,948,308 to Facey (1976). The Facey invention provides a foldable storm window or screen that has at least two rectangular panels that are joined together to form a structure larger than the window intended for protection. Each panel has a two-frame construction with the inner frame having brackets attached to it to which a pair of turnbuckles can be connected. The Facey invention also has resilient padding on the back perimeter of its outer frame to allow for irregularities in the building surface against which it will be placed, with its rectangular panels being made from thin pliable plastic, glass, or screen materials. The present invention differs from the Facey invention in that the present invention contemplates being positioned within the outermost groove of a double-hung window frame, not flat against the wall of the building adjacent to the window. Also, the present invention does not have a two-frame construction, brackets, or turnbuckles. Further, each of the rectangular panels in the Facey invention have a single turnbuckle connected behind it, while each of the opposing straps of the present invention extends across the rear surface of every connected foldable panel. As a result, the quick release of a few strap-connecting fasteners in the present invention would allow more rapid emergency evacuation of a building than a Facey invention having two or more turnbuckles, as even a few seconds longer delay in releasing the additional turnbuckles could mean the difference between a successful emergency escape and tragic consequences. Further, the present invention contemplates use of impact-resistant materials, including bullet-proof materials, as well as reinforcing bars, to protect a double-hung window from vandals and intruders, functions that the thin plastic, glass, and screen materials of the Facey invention would not be able to accomplish.
SUMMARY OF INVENTION
3. Objects and Advantages
The primary object of this invention is to provide a window protection device that is simple to use and can be removably secured within the outermost groove of a double-hung window frame by one adult of ordinary strength and coordination working from within the interior of a building so as to protect the window from such hazards as storm debris, vandalism, and entry by unauthorized persons. A further object of this invention is to provide a protective device for double-hung windows that is reusable and made from materials that will effectively protect windows from exposure to environmental elements for extended periods of time without undue deterioration itself from such elements. It is also an object of this invention to provide a protective device for double-hung windows that is lightweight and can be easily installed over both upstairs and downstairs windows without the use of tools or a ladder. A further object of this invention is to provide a protective device for double-hung windows that can be easily removed by the occupants of a building for quick evacuation through the window during emergencies but will otherwise remain securely in place as long as it is needed for window protection. It is also an object of this invention to provide a protective device for double-hung windows that when installed will not damage or permanently alter any portion of the window, window frame, weather-stripping around the window, or the building surfaces adjacent to the window. A further object of this invention is to provide a protective device for double-hung windows that can be folded into a compact configuration when not in use for easy storage within a readily accessible location, such as in a nearby closet or under a bed. It is also an object of this invention to provide a protective device for double-hung windows that requires little or no refurbishment between uses. A further object of this invention is to provide a protective device for double-hung windows that is sufficiently simple in design for inexpensive manufacture so it can be affordably priced for widespread homeowner use. It is a further object of this invention to provide a protective device for double-hung windows that can easily accommodate alternative materials to diversify its use, such as those materials which would make the protective device bullet-proof or one-way thermally conductive, or materials which would decoratively enhance the outer and inner surfaces of the protective panels.
As described herein, properly manufactured and properly installed, the present invention would provide a folding, multiple-panel device the edges of which can become secured within the outermost groove of a double-hung window frame so that the device can protect window sashes positioned behind it from damage due to wind, rain, vandalism, and unauthorized entry. The device could similarly protect horizontally sliding window sashes, provided a groove was present in the outer frame in front of the sash tracks for insertion of the protective panel perimeter edges. The device comprises at least two protective panels hinged together on their outside front surfaces which allows the protective panels to be easily folded and unfolded during both installation and removal of the device from its protective position. One embodiment of the present invention contemplates the protective panels being sandwiched between thinly-profiled outside panels which have centrally positioned accordion-type folds that facilitate the bending of each outside panel around the protective panels so that they all can be compactly folded together, with the thin outside panels functioning to protect the hinges and heads of the strap-connecting bolts from exposure to deteriorating elements, as well as protect the threaded end of the bolts and keep them from injuring people installing or removing the present invention, or scratching the paint on the window sashes or outer window frame. The edges of the protective panels may also have a resilient covering to keep them from scratching the installer or paint.
Each protective panel in a bi-folded embodiment of the present invention, or each of the two endmost protective panels in a series of three or more connected protective panels, has straps bolted to its inside back surface near the perimeter edge opposed to its hinged edge. The straps can be used as handles to facilitate the maneuverability of the protective panels during their installation, removal from a double-hung window frame, and transport between installation and storage sites. In one of the final steps of installation, the straps are each secured behind the window sashes to an opposing strap by use of a quick-release fastener, such as a clamping buckle. At the beginning of installation of the present invention in front of the panes of a double-hung window, the upper and lower window sashes are moved away from the outer frame toward the center of the window to create top and bottom openings. The entire present invention device is then inserted through the newly created top opening with the upper protective panel being positioned above the lower protective panel. The upper straps are then drawn rearward through the newly created top opening after which the lower protective panel is allowed to unfold so that the surface of the protective panels connected to the straps becomes positioned adjacent to the window glass. The upper window sash is then moved in an upward direction toward the outer frame and closed against the adjacent portion of the outer frame with the upper straps fixed therebetween and the upper edge of the upper protective panel positioned within the outermost groove of the outer frame. The lower straps are pulled through the newly created bottom opening under the lower window sash and inserted through the bottom-most rectangle of the clamping buckle, to connect the distal ends of opposed straps in each pair of straps to one another behind the window sashes with adjacent pairs of straps becoming essentially parallel to one another, after which the device is allowed to become centered in front of the double-hung window sashes with the edges of both its upper and lower protective panels becoming positioned within the outermost groove of the outer frame. The lower window sash is then moved in a downward direction and closed against the lower straps to fix the lower straps between the lower window sash and the outer frame. Opposing straps are then pulled taut to further secure the protective panels in place. The straps help to maintain the protective panels in their optimal positions during use and resist removal of the protective panels by anyone attempting to do so from the outside of the building. The protective panels are made from a durable, shatter-resistant material such as acrylic to provide an appropriate balance of a lightweight material that also has good abrasion resistance and impact strength. The protective panels can be transparent, translucent, or opaque, and may even contain surface decoration, depending on the homeowner's preference. The straps can also have surface decoration and be color coordinated to the decor of a room.
Since the installation is accomplished from the inside of a building, the present invention can usually be easily and rapidly installed over upstairs and downstairs windows by a single adult of average strength and coordination without the use of tools or a ladder. However, during windy conditions two people may be required to unfold the present invention and maneuver it into its usable position. In most instances two people would be required to install the present invention in front of horizontally-sliding window sashes since gravity would not favor installation as it does during placement of the present invention in front of a vertically operated double-hung window. Since neither tools nor a ladder is required for installation or removal and the opposing straps are connected to one another by quick-release fasteners, the present invention can be quickly removed if emergency egress through the double-hung window is required. The present invention can be used for storm protection on all windows of a house or used as an anti-theft device on downstairs or otherwise easily accessible windows when people are on vacation, for windows on vacant rental property, or at anytime they want an extra measure of security for their families. Bullet-proof materials and reinforcing bars can be used to further enhance the protective function of the present invention. Also, when not in use, the present invention can be folded into a compact configuration and easily stored within a nearby closet or under a bed in the room where it will be installed. Since the degree of transparency of the present invention can be selected by the homeowner, the use of transparent panels would allow the homeowner to leave the security device in place for extended periods of time and still let outside light come through the window. For example, parents may want continual protection for a window in a child's room throughout a storm season or when a child's room is on the first floor of the house, and such parents would be able to leave a transparent embodiment of the present invention in place throughout the entire anticipated duration of a storm season, or indefinitely, without significantly diminishing the amount of light entering the window and without creating a hazardous situation should emergency evacuation from the room through the window be required. The present invention is reusable, and its installation does not damage or permanently alter any part of a window, its frame, weatherstripping around the window, or the building surfaces adjacent to the window. The present invention can come in standard sizes or it can be custom-fit for connection to non-standard sizes of double-hung windows. Also, double-hung window frames could be manufactured with a larger outermost groove than is present in standard sizes of double-hung windows to allow installation of embodiments of the present invention having additional combinations of features which might cause an overall thickness exceeding one inch. Installation of the protective panels also provides a thermally insulating outer layer for double-hung windows and the panels can further comprise one-way thermal transfer materials, to either add heat to a room in a cold climate or keep afternoon sunlight from excessively heating a room in a warm climate. Further, since it is simple in design, the present invention would be cost effective to manufacture and as a result could be affordably priced for widespread homeowner use, as well as for use by tenants who might otherwise be concerned about losing a damage deposit if they were to permanently alter a window or adjacent walls by installing other types of security devices over windows.
The description herein provides preferred embodiments of the present invention but should not be construed as limiting its scope. For example, other embodiments of the folding security device for double-hung windows could have variations in the number of protective panels used; the overall size of each protective panel; the type of materials used to fabricate the protective panels; the degree of transparency of the materials used for the protective panels; the number of sheets sandwiched together to form each of the protective panels; the material from which the thin outside panels are made; the number of accordion-type folds in each thin outside panel; the number of straps attached to each protective panel; the width and thickness of the straps; the type of fasteners used to secure the hinges and straps to the protective panels; the number, size, and type of reinforcing bars used in association with the protective panels; and the type of quick-release fastener used to secure opposing straps together, other than those variations shown and described herein, may be incorporated into the present invention. Thus the scope of the present invention should be determined by the appended claims and their legal equivalents, rather than the examples given.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front detailed view of a first preferred embodiment of the present invention installed within the outermost groove of a double-hung window frame and having two hinged-together protective panels positioned in front of the double-hung window sashes, with the hinges attached to the outside front surfaces of the protective panels so that they fold away from the window sashes, and with straps attached to the inside back surfaces of the protective panels, as well as opposed upper and lower straps being connected together by clamping buckles behind the window glass.
FIG. 2 is a perspective view of the first embodiment of the present invention in a partially folded position, with its hinges positioned between the folding protective panels and the upper and lower straps disengaged from one another, and further with each upper strap having a quick-release clamping buckle attached near to its distal end.
FIG. 3 is a perspective view of the quick-release clamping buckle of the first embodiment of the present invention with one upper strap and one lower strap connected to opposing ends of the clamping buckle.
FIG. 4 is a side view of one of the hinges of the first embodiment of the present invention connecting the upper protective panel to the lower protective panel with arrows indicating the direction of protective panel folding, the hinge being connected to both the upper protective panel and the lower protective panel with bolts, and the hinge and the bolt heads shown being located between the two protective panels when the present invention is in its folded or partially folded configuration, while the nuts are shown being secured to the threaded ends of the bolts on the back sides of the upper protective panel and the lower protective panel.
FIG. 5 is a front view of the clamping buckle of the first embodiment of the present invention showing three rectangular holes therein through which the upper and lower straps are inserted during use, and with the clamping member of the buckle being visible through the two lowermost rectangular holes.
FIG. 6 is a side view of the clamping buckle of the first embodiment of the present invention with arrows showing the direction of movement that would occur in the top and bottom parts of the clamping member during quick-release of the buckle from a lower strap.
FIG. 7 is a back view of the clamping buckle of the first embodiment of the present invention showing the gripping bottom edge of the rearward pivoting clamping member of the buckle.
FIG. 8 is a perspective view of a second preferred embodiment of the present invention partially inserted sideways through an open double-hung window during either installation or removal, with the protective panels shown as being opaque.
FIG. 9 is a perspective view of the first embodiment of the present invention in a nearly unfolded position during installation, with the upper protective panel approximately parallel to the upper window sash and the upper window sash prepared to close against the upper straps, the upwardly pointing arrows indicating the direction of movement for the upper window sash to place pressure on the upper straps and temporarily hold them in position against the outer window frame while subsequent steps of installation take place, and with the lower panel shown in an unfolded configuration with one arrow indicating the downward direction of movement of one of the lower straps under the lower window sash needed for the lower strap to reach a clamping buckle so that the pairs of opposed straps can become secured taut behind the upper and lower double-hung window sashes.
FIG. 10 is a perspective view of a third embodiment of the present invention shown in a partially folded position, with both upper and lower protective panels having a three-ply configuration with several spaced-apart reinforcing bars sandwiched between two sheets of protective material, the reinforcing bars extending the full width of the protective panels, and also with the hinges positioned between the two folding protective panels, the upper and lower straps attached to the surfaces of the protective panels remote from hinge placement, and the upper and lower straps disengaged from one another.
FIG. 11 is an enlarged partial side view of a fourth embodiment of the present invention with both upper and lower protective panels having reinforcing bars and shown sandwiched between two separate more thinly profiled outside panels each having accordion-type folds that allow the outside panels to fold completely and in unison with the protective panels into a compact configuration for storage or transport, the direction of folding being shown by three arrows.
FIG. 12 is a full side view of the protective panels having reinforcing bars and positioned within the outermost groove of a double-hung window frame in front of the double-hung window sashes, with the upper and lower window sashes being locked in a closed position relative to one another, and opposed upper and lower straps fastened to one another in a taut configuration behind the window sashes by a clamping buckle.
FIG. 13 is a perspective view of a house with both upstairs and downstairs windows protected by the present invention.
FIG. 14 is a front view of a fifth embodiment of the present invention having three hinged together protective panels.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Several embodiments of the present invention are described herein which provide an additional measure of safety for double-hung windows against hazards such as inclement weather, vandalism or intruders (not shown). FIG. 1 shows a double-hung window comprising an upper sash 4 and a lower sash 6 which are positioned on separate but parallel tracks within an outer frame 2, better shown in FIG. 8. Upper sash 4 can be moved into a position below lower sash 6, but in their locked positions a substantial part of upper sash 4 is positioned above lower sash 6. Both upper sash 4 and lower sash 6 can be moved in upward and downward directions independently from each other in their separate tracks, typically with upper sash 4 moving in front of lower sash 6. Both sashes 4 and 6 have a layer of caulking material 8 to hold the glass 10 in a fixed central position within a perimeter framework traditionally made from wood. Outer frame 2 also has a downwardly and forwardly sloping window sill 14 the configuration of which is more clearly shown in FIGS. 8 and 9. A two-part window lock 12 having one part secured to the upper edge of lower sash 6 and its second part secured to the inside lower portion of upper sash 4, as more clearly shown in FIG. 12, can be used to lock upper sash 4 and lower sash 6 in a closed position relative to one another wherein the three non-locking edges of upper sash 4 and lower sash 6 each rest firmly against outer frame 2.
FIG. 1 also shows an upper protective panel 18 and a lower protective panel 16 connected together with two hinges 20. Depending upon the type of hinge used to attach upper panel 18 to lower panel 16, a minimal gap could exist between the bottom edge of upper panel 18 and the top edge of lower panel 16 and where necessary the gap having a size sufficient to allow upper panel 18 and lower panel 16 to fold essentially flat against one another into a compact configuration for storage. Upper panel 18 is positioned in front of upper sash 4 at a spaced-apart distance from the glass 10 within upper sash 4, and lower panel 16 is positioned in front of lower sash 6 at a greater spaced-apart distance from the glass 10 within lower sash 6, as better shown in FIG. 12. After installation the non-hinged edges of upper panel 18 and lower panel 16 are securely positioned within the outermost groove of outer frame 2, which is parallel to, but separate from, the track for upper sash 4, also more clearly shown in FIG. 12. Although the preferred embodiment shown in FIG. 1 utilizes two protective panels 16 and 18, it is contemplated that more than two protective panels may be used, as long as the overall size of the present invention is sufficiently large to cover both upper sash 4 and lower sash 6 while simultaneously not overly large so that the non-hinged edges of upper panel 18 and lower panel 16 cannot be easily maneuvered to fit within the outermost groove of outer frame 2.
In FIG. 1, upper panel 18 and lower panel 16 are shown as being transparent so as to protect sashes 4 and 6 while still allowing light (not shown) to pass through window glass 10. However, it is also contemplated for upper panel 18 and/or lower panel 16 to have varying degrees of transparency from translucent to opaque for, each to comprise a different degree of transparency, or even for each to comprise decorative surface markings to enhance their aesthetic appeal according to the homeowner's preference. Upper panel 18 and lower panel 16 could also have surface markings of sufficient size and composition to keep birds from flying into them and becoming injured. In the preferred embodiment shown in FIG. 1, it is contemplated for upper panel 18 and lower panel 16 to be fabricated from a resilient material such as acrylic which is lightweight and yet provides good abrasion resistant and impact strength characteristics. However, other materials, such as materials incorporating recycled plastics, are also contemplated. Upper panel 18 and lower panel 16 can each be made from a single-ply sheet or multiple sheets bonded together. Reinforcing bars 34, shown in FIGS. 10-12 can also be integrated into a single-ply sheet or sandwiched between separate or multiple sheets to form panels 16 and 18. Although not shown performing such a function, the present invention is also contemplated for protection of horizontally operating two-sash sliding windows. While gravity helps in the installation of the present invention in front of vertically operated double-hung window sashes 4 and 6 and generally allows installation by one adult of average strength and coordination unless windy conditions are present, gravity would not assist in the installation of the present invention in front of horizontally operated sliding windows, and in most instances it would take two people to perform such an installation. A large child with the strength and coordination of an average adult should be capable of at least removing the present invention during emergencies from both horizontally and vertically oriented window sashes. It is contemplated for both panels 16 and 18 to have a minimum thickness of one-half inch, however it is preferred that the minimum thickness be at least three-fourths of an inch for enhanced impact resistance against storm generated debris, vandals, and intruders. For standard sizes of double-hung windows, the outermost groove in outer frame 2 places a one-inch maximum limit on the thickness of upper panel 18 and lower panel 16. In the alternative, for custom-sized double-hung windows, the outermost groove in outer frame 2 could be made to accommodate a desired panel thickness greater than one inch. For the simplest embodiment of the present invention having only two single-ply panels each approximately one-half of an inch in thickness and dimensioned for the smallest standard perimeter dimension of a double-hung window, it is contemplated that the present invention with straps 22 and 24 attached thereto would weight approximately five pounds. It is contemplated for other simple embodiments of the present invention to weigh no more than ten pounds so that an adult of average strength and coordination could easily handle it to install and successfully remove it from the outermost groove of outer frame 2.
FIG. 1 also shows hinges 20 attached with fasteners 26 to the outside, front surfaces of upper panel 18 and lower panel 16 in such a way that upper panel 18 can be folded into a position substantially parallel to lower panel 16 for compact storage. The heads of fasteners 26 are shown positioned in front of each hinge 10. Although not shown in FIG. 1, but shown in FIG. 4, fasteners 26 extend though hinges 20 and either upper panel 18 or lower panel 16, with one hexagonal nut 32 connected to each fastener 26 to secure its threaded end to the rear surface of either panel 16 or 18. When it is anticipated that hinges 20 will be exposed to readily deteriorating forces, such as the salt spray from a beach, it is contemplated for hinges 20 to be made from corrosion-resistant materials, such as stainless steel, or to be made from other materials coated with a corrosion-resistant film. FIG. 1 shows the first embodiment of the present invention having two hinges 20, however, it is contemplated that different quantities of hinges and hinges having different configurations may also be used. FIG. 1 shows three fasteners 26 attaching each hinge 20 to lower panel 16 and an additional three fasteners 26 attaching each hinge 20 to upper panel 18, however the use of three fasteners 26 for each such connection is not critical to the present invention. In the present invention it is contemplated to have a minimum of two fasteners 26 for the attachment of each hinge 20 to a protective panel, such as upper panel 18 or lower panel 16, so that folding and unfolding forces are distributed across more than one connection point to strengthen the attachment between adjacent protective panels. Also, fasteners 26 are not limited to bolts, as shown in FIG. 1, and rivets (not shown) or other vandal and intruder-resisting means of attaching hinges 20 to panels 16 and 18 are within the scope of the present invention.
FIG. 1 also shows two upper straps 22 attached to the inside, back surface of upper panel 18, and two lower straps 24 attached to the inside, back surface of lower panel 16. At a minimum, upper straps 22 and lower straps 24 should be made from a material sufficiently strong to resist gale force winds, such as nylon, and can be manufactured from materials having a variety of colors as well as decorative patterns thereon to complement the decor of a room. Although it is contemplated for the number of upper straps 22 to be identical to the number of lower straps 24, and for each upper strap 22 to be placed into a position opposed to one lower strap 24, the total number of straps 22 and 24 used is not critical as long as the number of straps 22 and 24 is sufficient to securely maintain panels 16 and 18 in their optimally protective positions in front of upper sash 4 and lower sash 6 with the non-hinged edges of upper panel 18 and lower panel 16 hidden within the outermost groove of outer frame 2. Also, although FIG. 1 shows each upper strap 22 having two fasteners 26 connecting it to upper panel 18 and each lower strap 24 having two fasteners 26 connecting it to lower panel 16 to evenly distribute the weight of upper panel 18 and lower panel 16 during manipulation of straps 22 and straps 24 during installation and removal of the present invention from outer frame 2, it is contemplated for the connection of straps 22 and 24 to panels 18 and 16, respectively, to have more fasteners 26 per strap, but at a minimum no less than two. The heads of fasteners 26 connect hinges 20 against the front surfaces of upper panel 18 and lower panel 16 and as shown in FIG. 4 the threaded end of each fastener 26 is secured by a hexagonal nut 32 attached against the sash-facing surface of one of the upper straps 22 or one of the lower straps 24. In the preferred embodiment of the present invention shown in FIG. 1, upper straps 22 and lower straps 24 have a width dimension between approximately two and three inches and a length dimension of approximately thirty-six inches. However, the present invention is not restricted to such length and width dimensions, since the length of straps 22 and 24 would be proportioned to the combined height of upper panel 18 and lower panel 16. Also, although not shown, upper strap 22 and lower strap 24 can be bonded to the rear surfaces of panels 16 and 18, respectively, in addition to the use of fasteners 26 to strengthen the attachment of straps 22 and 24 to panels 16 and 18.
During installation of the present invention for protection of double-hung window glass 10, upper sash 4 and lower sash 6 are moved toward the center of outer frame 2 to create openings between sashes 4 and 6 and outer frame 2, and upper straps 22 and lower straps 24 are drawn through the newly created openings above upper sash 4 and below lower sash 6, respectively, to be secured to an opposing strap 22 or 24 with a clamping buckle 28. The connection of upper straps 22 to lower straps 24 is made behind window glass 10 from the inside of a building, such a house 36 shown in FIG. 13. In the preferred embodiment shown in FIG. 1, and as is more clearly shown in FIG. 2, although not limited to such attachment, it is contemplated for clamping buckle 28 to remain attached to upper strap 22 when straps 22 and 24 are separated. Also, although the present invention utilizes a clamping buckle 28 to secure upper straps 22 and lower straps 24 to one another, it is contemplated that other types of quick-release fasteners may be used to secure opposing upper straps 22 and lower straps 24 to one another, such as heavy duty hook-and-pile types of fasteners (not shown). FIG. 1 further shows the three non-hinged edges of upper panel 18 and lower panel 16 being covered by a resilient edging material 30, such as but not limited to rubber, foam, or other materials commonly used for weatherstripping purposes. The use of resilient edging material 30 is not critical to the present invention, but it prevents the non-hinged edges of panels 16 and 18 from scratching an installer (not shown) or any surface finish on outer frame 2 during their transport and handling. Resilient edging material 30 also fulfills a weatherstripping function and it improves the fit of panels 16 and 18 within the outermost groove of outer frame 2 when the present invention is retrofitted to an existing double-hung window.
FIG. 2 shows the first embodiment of the present invention in a partially folded configuration with upper panel 18 connected to lower panel 16 by two hinges 20. A connection between panels 16 and 18 having one long hinge extending the full width of panels 16 and 18, as well as a connection having more than two hinges 20, is also contemplated. FIG. 2 shows two upper straps 22 are laterally connected on the edge of upper panel 18 opposed to its hinged edge, with two lower straps 24 also laterally connected on the edge of lower panel 16 opposed to the edge connected to hinges 20. FIG. 2 also shows straps 22 and 24 positioned against the outside surfaces of panels 18 and 16 respectively, with hinges 20 being connected to the inside folded surfaces of upper panel 18 and lower panel 16. The heads of two fasteners 26 are shown positioned on the inside folded surface of lower panel 16 and used to connect lower straps 24 to the inside folded surface of lower panel 16. FIG. 2 also shows nuts 32 attached to the threaded ends of all of the fasteners 26 used for connecting both hinges 20 and upper straps 22 to upper panel 18. Although not shown, nuts 32 can have any configuration appropriate to its function of securely positioning one fastener 26 to either a hinge 20, an upper strap 22, or a lower strap 24, and then further to either upper panel 18 or lower panel 16. FIG. 2 also shows resilient edging material 30 attached to the three non-hinged perimeter edges of both upper panel 18 and lower panel 16, as well as a clamping buckle 28 attached near to the distal end of each upper strap 22. Once lower straps 24 are released from buckle 28, upper panel 18 can be folded downward to a position that is substantially parallel to lower panel 16 for insertion through outer frame 2 during installation, removal from outer frame 2, or storage. When the present invention is in the compact configuration shown in FIG. 2, it can be more easily stored in a household attic, garage, basement, under a bed, or in a closet near to the double-hung window targeted for protection.
FIG. 3 shows upper strap 22 connected through both of the rectangular openings in the top part of a clamping buckle 28, with lower strap 24 inserted through a single lower rectangular opening in the bottom part of clamping buckle 28. Although the top and bottom parts of clamping buckle 28, as well as the three openings in clamping buckle 28 are shown to have a rectangular configuration, such rectangular configurations are not critical to the present invention. In the preferred embodiment of clamping buckle 28 shown in FIG. 3, the distal end of lower strap 24 would be threaded through the front side of the bottom part of clamping buckle 28, where it would extend downwardly various distances beyond the lower edge of the bottom part of clamping buckle 28 behind the proximal end of lower strap 24. A clamping member not visible in FIG. 3, but shown in FIGS. 5-7, would securely grip the distal end of lower strap 24 to prevent it from changing length when lower strap 24 is pulled taut during use. In contrast, the distal end of upper strap 22 is threaded from the back side of clamping buckle 28 into the bottom opening in the top part of clamping buckle 28. The distal end of upper strap 22 would then be inserted from the front side of clamping buckle 28 rearwardly through the top opening in the top part of clamping buckle 28 so as to extend upwardly beyond the top part of clamping buckle 28 in front of the proximal end of upper strap 22. The size of clamping buckle 28 should correspond to the chosen widths of upper strap 22 and lower strap 24 so that upper strap 22 and lower strap 24 remain firmly fixed within clamping buckle 28 without lateral movement during use. Also, the strap fastening means of the present invention is not limited to use of the quick-release clamping buckle 28 shown in FIG. 3 and it is considered within the scope of the present invention to have other quick-release fastening means to connect each upper strap 22 to an opposing lower strap 24, as long as such strap fastening means is able to hold opposing straps 22 and 24 for extended periods of time in fixed taut positions relative to the other behind upper sash 4 and lower sash, even when the present invention is subjected to winds (not shown) approaching gale force strength so that panels 16 and 18 can remain in their optimal protective positions to protect sashes 4 and 6.
FIG. 4 shows an enlarged view of one hinge 20 of the first embodiment of the present invention connected between upper panel 18 and lower panel 16. Three fasteners 26 are positioned through each half of hinge 20 and either upper panel 18 or lower panel 16. FIG. 4 shows the heads of fasteners 26 extending beyond the inside folded surfaces of upper panel 18 and lower panel 16, with the threaded ends of fasteners 26 extending beyond the outside folded surface of either upper panel 18 or lower panel 16 and secured thereto with a hexagonal nut 32. Although FIG. 4 shows three fasteners 26 and three nuts 32 securing each half of hinge 20 to either upper panel 18 or lower panel 16, the number of fasteners 26 and nuts 32 is not critical as long as the number of fasteners and nuts is sufficient to securely hold hinge 20 against both upper panel 18 and lower panel 16. However, in the preferred embodiment it is contemplated for the present invention to have at least two fasteners 26 and two nuts 32 connecting each half of hinge 20 to either upper panel 18 or lower panel 16. Also, it is not critical for nuts 32 to be hexagonal nuts, and nuts 32 can have any configuration which fulfills the needed function of securing hinge 20 to either upper panel 18 or lower panel 16. Further, the configuration of the head of each fastener 26 is not critical, however, the heads of fasteners 26 should not extend beyond the outer surface of hinges 20 an undue amount so as to interfere with the folding of upper panel 18 and lower panel 16, and the configuration of the heads of fasteners should be such that minimizes the possibility of tampering by a potential burglar or other intruder (not shown) and removal of panels 16 and 18 from in front of window sashes 4 and 6. Neither the thickness nor the configuration of hinge 20 is critical to the present invention, however, hinge 20 should be configured to allow upper panel 18 and lower panel 16 to fold nearly flat against one another with upper panel 18 and lower panel 16 substantially parallel to each other after folding so that the present invention can be easily stored between uses.
FIGS. 5, 6, and 7 provide front, side, and back views, respectively, of the clamping buckle 28 of the first embodiment of the present invention. FIG. 5 shows clamping buckle 28 having a top part with two rectangular holes and a bottom part having a single rectangular hole with a clamping member pivotally fixed to the back side of clamping buckle 28. FIG. 6 has two arrows showing the direction of movement of the upper and lower portions of the centrally pivoting clamping member relative to the remainder of clamping buckle 28 when clamping buckle 28 is released from a lower strap 24. FIG. 7 shows the bottom edge of the pivoting clamping member having a gripping saw-toothed type of configuration for non-slip engagement with lower strap 24 to allow opposing upper straps 22 and lower straps 24 to be pulled taut behind window sashes 4 and 6 and remain taut during use. Although not shown, it is within the scope of the present invention to have any type of quick-release means other than clamping buckle 28 which can connect an upper strap 22 to an opposing lower strap 24 and maintain straps 22 and 24 firmly secured together during use, such as but not limited to a heavy duty hook-and-pile type of fastener.
FIGS. 8 and 9 show a second opaque embodiment of the present invention wherein upper panel 18 and lower panel 16 are being installed in front of upper sash 4 and lower sash 6 of a double-hung window. The basic steps of installation shown in FIGS. 8 and 9 are applicable to all embodiments of the present invention. When they are removed from storage, upper panel 18 and lower panel 16 are in a folded configuration wherein each is substantially parallel to the other, with upper straps 22 each having one clamping buckle connected to its distal end and lower straps 24 disengaged from clamping buckle 28. Hinges 20 are positioned between upper panel 18 and lower panel 16 against the inside folded surfaces of panels 16 and 18, with straps 22 and 24 being laterally attached on the outside folded surfaces of upper panel 18 and lower panel 16, respectively, in opposing positions to one another. FIG. 8 also shows caulking material 8 attached to upper sash 4 and FIG. 9 shows fasteners 26 connecting upper straps 22 to the upper protective panel, shown as number 18 in FIG. 8. Although not shown, straps 22 and 24 may also be attached to panels 16 and 18 with bonding agents or adhesives to further secure attachment therebetween. Prior to installation and with both panels 16 and 18 remaining in a folded configuration and essentially parallel to one another, upper panel 18 is placed above lower panel 16. Both upper sash 4 and lower sash 6 must be moved to the center of outer frame 2 before installation to create an upper opening through which upper straps 22 can be inserted and a lower opening through which lower straps 24 can be inserted so that upper straps 22 and lower straps 24 can be drawn through the upper and lower openings and connected to one another behind upper sash 4 and lower sash 6. As shown in FIG. 8, an installer (not shown) while holding onto one of the non-hinged, non-strap bearing ends of both upper panel 18 and lower panel 16 from within the building, such as house 36 shown in FIG. 13, will insert the opposed non-hinged, non-strap bearing ends of panels 16 and 18 through the upper opening between upper sash 4 and outer frame 2, so that upper panel 18 and lower panel 16 extend beyond outer frame 2. While being manipulated and positioned fully beyond outer frame 2, the installer would grasp upper straps 22 and allow gravity (not shown) to cause lower panel 16 to unfold downwardly in front of lower sash 6 with hinges facing away from lower sash 6. The unfolded combination of panels 16 and 18 will then create an essentially planar structure in front of upper sashes 4 and lower sash 6. The upper edge of upper panel 18 is then maneuvered to fit within the outermost groove of outer frame 2. While the installer holds onto at least one upper strap 22, but preferably two upper straps 22, upper sash 4 is moved in an upward direction toward outer frame 2, as shown by the arrows in FIG. 9, until upper sash 4 contacts upper straps 22 and closes them against outer frame 2 to secure upper straps 22, as well as upper panel 18, in a substantially fixed position. Lower straps 24 can then be captured by the installer and drawn rearwardly over window sill 14 and through the opening between lower sash 6 and outer frame 2. Using lower straps 24 the bottom edge of lower panel 16, as well as the sides of both panels 16 and 18 can then be maneuvered into the outermost groove in outer frame 2 and panels 16 and 18 moved vertically and horizontally as needed to approximately center them within outer frame 2, after which lower sash 6 can be moved downwardly within its track until lower sash 6 closes on lower straps 24 to secure lower straps 24, as well as lower panel 16, in a substantially fixed position. Lock 12 can then be engaged between sashes 4 and 6 to further secure straps 22 and 24 in fixed positions against outer frame 2. The distal ends of each lower strap 24 is then inserted through the lower rectangular opening in a clamping buckle 28 attached to the distal end of an opposed upper strap 22 so that opposing straps 22 and 24 become connected vertically behind the window glass 10. Lower straps 24 are then pulled taut relative to upper straps 22 so as to provide an additional measure of security in maintaining upper panel 18 and lower panel 16 in their optimally protective positions in front of upper sash 4 and lower sash 6 to protect sashes 4 and 6 against storm debris and intruders.
Removal of the present invention from outer frame 2 is also fast and easily accomplished. The person removing panels 16 and 18 would first disengage lock 12, then move both sashes 4 and 6 away from outer frame 2 to re-create the opening between upper panel 18 and outer frame 2, as well as the second opening between lower panel 16 and outer frame 2. The installer would then activate the pivotally attached clamping members of each clamping buckle 28 to successively separate opposing straps 22 and 24 from one another. While holding onto at least one upper strap 22 when the last clamping member is pivoted, the installer would then use one or more upper straps 22, preferably at least two, to hold onto upper panel 18 while the installer turns upper panel 18 at an oblique angle relative to outer frame 2 and further reaches beyond outer frame 2 to capture one or more lower straps 24. While holding onto at least one upper strap 22 and one lower strap 24 with one hand, the installer would then grasp the near end of panels 16 and 18 directly with his or her other hand and use both hands to place panels 16 and 18 into a substantially horizontal position so that panels 16 and 18 can be drawn back through the opening between upper sash 4 and outer frame 2. Once panels 16 and 18 were substantially situated behind outer frame 2, the installer could use one hand to also move the remaining straps 22 and 24 behind sashes 4 and 6. After removal of the present invention, a screen (not shown) closure could be centrally positioned within the outermost groove of outer frame 2 in place of panels 16 and 18. As with installation, removal of the present invention can usually be performed by one person of average strength and coordination without the use of tools or a ladder. In the alternative, during emergencies the person removing the present invention could let go of upper straps 22 once upper sash 4 and lower sash 6 have been moved away from outer frame 2, and cause the present invention to fall to the ground surface below the double-hung window. Easy removal of the present invention also makes panels 18 and 16 easier to clean than permanently installed storm windows (not shown).
FIG. 10 shows a third embodiment of the present invention having upper panel 18 and lower panel 16 each with a three-ply construction consisting of a plurality of reinforcing bars 34 sandwiched between inner and outer impact-resistant layers of material, such as PLEXIGLAS®. It is also contemplated that bars 34 can be integrated into the structure of upper panel 18 and lower panel 16 when they are made from one-ply sheets. The number, type, configuration, and size of reinforcing bars 34 can vary, but preferably bars 34 extend the full width of upper panel 18 and lower panel 16. FIG. 10 shows upper panel 18 and lower panel 16 in a partially folded configuration so that hinges 20 are positioned between upper panel 18 and lower panel 16, and straps 22 and 24, as well as nuts 32, are secured to the outside folded surfaces of upper panel 18 and lower panel 16. Bars 34 provide an additional measure of security to a home, since bars 34 act to make it more difficult for storm debris, vandals, and intruders to break through upper panel 18 and lower panel 16. Although FIG. 10 shows bars 34 in their preferred substantially horizontal position within panels 16 and 18, it is also contemplated for bars 34 to be placed in alternative spaced-apart orientations, such as vertically intersecting with one another in a latticed configuration, or at oblique angles relative to the perimeter edges of upper panel 18 and lower panel 16. The configuration and attachment of hinges 20, upper straps 22, lower straps 24, and resilient edging material 30 to panels 16 and 18, as well as the attachment of clamping buckles 28 to lower straps 24, is contemplated to be the same as in previously disclosed embodiments. Resilient edging material 30 is shown to cover the non-hinged edges of panels 16 and 18, and extend a predetermined distance over both their inside and outside folded surfaces of both panels 16 and 18. The extension of resilient edging material 30 must be sufficient to allow resilient edging material 30 to remain securely in place to fulfill its function, that of preventing the protected edges from injuring an installer (not shown) or from scratching the finished surface of sashes 4 and 6, or outer frame 2, during installation and other handling of the present invention.
FIG. 11 illustrates the center portion of a fourth embodiment of the present invention wherein the three-ply construction of FIG. 10 is further encased between two thinly profiled outside panels 40, each having a plurality of centrally located accordion-type folds 42 adjacent to hinge 20. Although not shown, it is contemplated for the non-visible extensions of both outside panels 40 to have a planar configuration that is positioned substantially parallel to both upper panel 18 and lower panel 16. It is also contemplated for both outside panels 40 to be made from materials that would protect hinges 20, fasteners 26, and nuts 32 from rust, corrosion, vandalism, and tampering by potential intruders, as well as protect an installer (not shown) from being scratched by fasteners 26 or nuts 32 while handling upper panel 18 and lower panel 16. It is contemplated that folds 42 directly facing hinge 42 will condense when the present invention is folded for installation, removal, and storage. In contrast, it is contemplated that folds 42 which are remote from hinge 20 will expand around upper panel 18 and lower panel 16 when the present invention is folded. The number of folds 42 is not critical, but it is contemplated in the preferred embodiment for the number of folds 42 on the outside panel 40 directly facing hinges 20 to be less than the number of folds 42 on the outside panel 40 remote from hinges 20. Outside panels 40 may be secured to the perimeter edges of panels 16 and 18 with bonding agents, or secured by similar attachment to resilient edging material 30. FIG. 11 shows fasteners 26, nuts 32, and hinge 20, as well as the hinged edges of panels 16 and 18, all positioned between folds 42. In the preferred embodiment, although not critical, it is contemplated for the outside panels 40 to be made from a thin tear-resistant plastic, perhaps even recycled material. Outside panels 40 may be transparent, translucent, or opaque. Outside panels 40 may also be made from colored materials, as well as materials having surface decoration.
FIG. 12 shows the present invention secured within the outermost groove in outer frame 2, in front of upper sash 4 and lower sash 6, where a screen (not shown) might otherwise be positioned for use. Window glass 10 is shown centered within both upper sash 4 and lower sash 6. Upper strap 22 is inserted between the uppermost part of outer frame 2 and the top surface of upper sash 4, with upper sash 4 closed against upper strap 22 to secure upper strap 22 against outer frame 2 while set within the wall structure of house 36. Similarly, lower strap 24 is inserted between the window sill 14 of outer frame 2 and the bottom surface of lower sash 6, with lower sash 6 closed against lower strap 24 to secure lower strap 24 against window sill 14. Although for simplicity window sill 14 is illustrated in FIG. 12 to have a substantially horizontal orientation, in actuality window sill 14 would have the forwardly and downwardly sloping configuration shown in FIGS. 8 and 9. Also, as an extra measure of security, lock 12 is engaged to prevent movement of upper sash 4 relative to lower sash 6 while the present invention is in place. Strap 22 and 24 are connected together with clamping buckle 28 and pulled taut behind upper sash 4 and lower sash 6. In addition, FIG. 12 shows bars 34 in spaced-apart positions within upper panel 18 and lower panel 16, with resilient edging material 30 positioned on the upper and lower edges of upper panel 18 and lower panel 16, respectively. The number of bars 34 used in panels 16 and 18 should be sufficient to provide the level of protection desired by the user, but not exceed the number that would make panels 16 and 18 too heavy to be easily maneuverable. Upper strap 22 is connected by fasteners 26 to upper panel 18, on the back side of upper panel 18 between upper panel 18 and upper sash 4, near to the upper edge of upper panel 18. Similarly, lower strap 24 is connected by fasteners 26 to lower panel 16, on the back side of lower panel 16 between lower panel 16 and lower sash 6, near to the lower edge of lower panel 16. FIG. 12 shows panels 16 and 18 having essentially identical height dimensions with hinge 20 connected between the lower edge of upper panel 18 and the upper edge of lower panel 16. However, it is also within the scope of the present invention for the height dimensions of panels 16 and 18 to be different, particularly when the present invention has more than two protective panels so that all of the protective panels can fold together into a compact configuration for storage. FIG. 12 shows all nuts 32 attached to fasteners 26 holding hinge 20, upper strap 22, and lower strap 24 against panels 16 and 18 in positions located between panels 16 and 18 and sashes 4 and 6, respectively, so as to be inaccessible to a person outside of house 36 attempting to remove the present invention from its protective position.
FIG. 13 shows three present invention devices having upper panel 18, lower panel 16, and two hinges 20 installed over two upstairs windows and one downstairs double-hung window in house 36 to protect house 36 from intruders attempting to gain entry through the double-hung windows. FIG. 13 also shows a fourth present invention device during installation or removal from outer frame 2, with lower straps 24 separated from upper straps 22. Although it is contemplated for transparent embodiments of the present invention to be used for storm debris protection over upstairs windows in house 36, and for translucent or opaque embodiments of the present invention to be used for protection against intruders, any combination of present invention embodiments can be used to cover the windows on house 36, including those comprising bullet-proof materials and bars 34. Also, the present invention can be made in standard dimensions to protect commonly used sizes of double-hung windows, or custom made to fit non-standard sizes of windows. The present invention would also be successful in protecting double-hung windows that are secured in a bay window configuration since no separate hardware would be required on the bay window frame. Installation of the present invention is rapid and no professional person is required, only an adult of average strength and coordination. Once the protective panels, such as upper panel 18 and lower panel 16, are lowered into position, in the preferred embodiment, simple clamping buckles 28 or other quick-release fasteners (not shown), such as heavy duty hook-and-pile fasteners, are used to connect each upper strap 22 to an opposing lower strap 24. Since the present invention is purchased once and reused many times with little refurbishment between uses, and without damage or alteration to the windows or walls of house 36, the present invention is a cost effective way in which to protect double-hung windows.
FIG. 14 shows a fifth embodiment of the present invention having three protective panels, an upper protective panel 18, a middle protective panel 44, and a lower protective panel 16 positioned in front of a double-hung window comprising an upper sash 4, a lower sash 6, an outer frame 2, glass 10, caulking material 8, and a window lock 12 securing upper sash 4 in a fixed position relative to lower sash 6. Two hinges 20 connect the bottom edge of upper protective panel 18 to the top edge of middle protective panel 44. A second pair of hinges 20 connects the bottom edge of middle protective panel 44 to the top edge of lower protective panel 16. Fasteners 26 connect hinges 20 to upper protective panel 18, middle protective panel 44, and lower protective panel 16. Although FIG. 14 shows upper protective panel 18, middle protective panel 44, and lower protective panel 16 all having approximately the same dimension and configuration, it is considered within the scope of the present invention for upper protective panel 18, middle protective panel 44, and lower protective panel 16 to have different height dimensions. FIG. 14 further shows resilient edging material 30 attached to the non-hinged edges of upper protective panel 18, middle protective panel 44, and lower protective panel 16, with the bottom edge of resilient edging material 30 positioned against window sill 14. In addition, FIG. 14 shows two upper straps 22 each connected to an opposed lower strap 24 with a buckle 28 and pulled taut behind glass 10 ready for use. Installation and removal of the fifth embodiment shown in FIG. 14 is similar to that of the first embodiment shown in FIG. 1, with gravity being used to assist the unfolding of middle protective panel 44 and lower protective panel 16, and their positioning in front of lower sash 6.
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An aesthetically-pleasing foldable, reusable security device and method for protecting double-hung windows from storm debris hazards and vandalism, wherein the perimeter edges of the device fit within the outermost groove of a double-hung window frame and can be easily installed and removed by one adult of ordinary strength and coordination standing behind the window. The device also protects the building against unauthorized entry and burglary, and is particularly useful for protecting upstairs windows since it requires no pre-installation steps or hardware, no professional installation, no tools, no ladder, and its installation does not permanently alter or damage the window or adjacent building surfaces. The device has at least two protective panels with two or more hinges attached between the front surfaces of adjacent panels which allow them to fold substantially parallel to one another in a compact configuration for storage, and unfold again into an essentially planar configuration for use. Straps are attached to the back surfaces of the two endmost panels, drawn around the window sashes and secured by them against the outer window frame, and then pulled taut behind the closed and locked sashes with a quick-release fastener. The protective panels may be transparent, translucent, or opaque, depending on the homeowner's preference or need, and the straps and panels can be color coordinated and can comprise decorative designs for enhanced aesthetic appeal. Also, the panels may optionally contain reinforcing bars, resilient edging and bullet-proof materials, one-way heat transfer materials, corrosion-resistant films, and multiple-layered panel construction.
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BACKGROUND OF THE INVENTION
The invention relates to a special arrangement of a vertical axis rotary looptaker for readily replenishing the thread supply of a double lockstitch sewing machine, which is a part of an automated sewing device.
Sewing devices for sewing a fabric cut on a workpiece part by means of two parallelly extending stitchlines, which are received in a controlled workpiece clamping plate, commonly are provided with a double-needle sewing machine having two vertical axis rotary looptakers carrying a thread supply. In order to replenish the thread supply, the operator must clear the table, i.e. removing the workpiece respectively transferring a clamped workpiece by means of the feeding unit into a position as not to interfer with the thread supply replenishing procedure. Additionally, the operator must remove the slide plates covering the looptakers.
To indicate a required bobbin change sewing devices of this type are equipped with workpiece counters. Nevertheless, it occurs, that the looptaker thread supply is consumed before the workpiece is finished. In such case, the process of thread supply replenishment becomes even more difficult, since the operator must trigger the built-in thread trimmer to disconnect the needle thread from the partially sewn workpiece prior to removing the workpiece.
As obvious, the thread replenishing procedure is a time consuming process. Furthermore, a special control mechanism is necessary to displace the workpiece clamp as the sewing machine remains inoperative, in order to clear the looptakers. Moreover, the sliding of a partially sewn and even cut workpiece by the workpiece clamp on a workplate presents a problem, since the workpiece parts tend to move relatively to each other.
In the production of setting patch pockets on garments similar automated sewing devices have been applied. Such a sewing device in general is installed with a single-needle double lockstitch machine, which has a horizontal axis rotary looptaker. For this reason, independently of the workpiece clamp position, the looptaker always is easily accessible for thread supply replenishment.
SUMMARY OF THE INVENTION
It is an object of this invention to find an arrangement of a vertical axis rotary looptaker installed in a sewing machine of a sewing device as aforesaid, which allows an easy access to the looptaker for replenishing the thread supply in a short time.
It is another object of this invention to avoid a displacement of a workpiece feeding unit in order to replenish the looptaker thread supply.
A further object of the present invention is to provide a sewing device, which has a plane work table without any edges or recesses besides the stitch hole, causing an increase of friction and distorting the workpieces moved by the feeding unit on the work table.
The foregoing is realised by arranging the vertical axis rotary looptaker of a sewing device in a tiltable manner. In a preferred embodiment the saddle, which carries the looptaker, is shifted and locked by a shifting mechanism.
Other objects, features and advantages of the invention will be described in connection with the drawings and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the sewing device including a sewing machine incorporating the present invention;
FIG. 2 is a top plan view of the sewing device corresponding to FIG. 1;
FIG. 3 is an enlarged front elevation of the sewing machine illustrated in FIGS. 1 and 2;
FIG. 4 is an enlarged view of the sewing machine, partially broken away, in direction IV of FIG. 3;
FIG. 5 is a section taken along line V--V of FIG. 4;
FIG. 6 is a side view of the sewing machine, partially broken away, in the direction VI of FIG. 3;
FIG. 7 is a side view of the sewing machine as FIG. 6, however showing the saddle with the looptaker in a tilted position; and
FIG. 8 shows a view similar to FIG. 6, however with another saddle-shifting mechanism; and
FIG. 9 partially shows the bed of the sewing machine with the looptaker arrangement in a transparent perspective view.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particular to the drawings, a sewing machine 1 is received on a work supporting plate 2 fastened by means of studs 3 to a plate 4, which is mounted on posts 5 arranged on a stand 6 (FIG. 1). The stand 6 is provided with a motor 7 having a pulley 8 for driving a pulley 10 by means of a belt 9. The pulley 10 is secured to a transmission shaft 11 received in bearings 12, which are fastened to the stand 6. As illustrated in FIGS. 1 and 2, the transmission shaft 11 carries a clutch coupling 13, which is provided with a pulley 14 for driving by means of a belt 15 an intermediate pulley 16 arranged on a shaft 17, which is received in a bearing 18 fastened to the stand 6, in order to drive the sewing machine 1 via a belt 19. The transmission shaft 11 further carries a pulley 20 cooperating with a pulley 21 by means of a belt 22.
A reduction gear 23 has an input shaft 24 for the pulley 21 and is fastened to the stand 6. The reduction gear 23 further has a vertical output shaft 25, which is provided with a flange 26 for receiving a control disk 27.
The stand 6 is further provided with bearings 28 and 29, which pivotally receive the ends of levers 30 and 31, each having a cam follower 32 and 33 for cooperating with cam grooves 34 and 35, which are located in the control disk 27. The free end of the lever 30 is linked to one end 35 of a drive lever 36, whereas the free end of the lever 31 is hinged to a connecting lever 37, the free end of which is linked to the drive lever 36.
Furthermore, the drive lever 36 is provided with studs 38 and 39 for carrying a workpiece clamping mechanism 40 by means of screws 41 and 42. The workpiece clamping mechanism 40 consists of a bracket 43 installed with an arm 44 (FIG. 1), which reaches beneath the plate 4 and has thrust bearings 45 abutting against the plate 4, and an upstanding bearing 46 for hingedly receiving a bolt 47 supporting a double-armed lever 48, one arm 49 of which is linked to a pneumatic cylinder 50 jointly resting on the bracket 43, whereas the other arm 51 of which rests against the workpiece supporting plate 2 clamping a workpiece 52. The other arm 51 is further provided with a plate 53, which has a recess 54 shaped according to the configuration of a stitch pattern 55 to perform stitching (FIG. 2).
As illustrated in FIG. 3, the sewing machine 1 has a bracket arm 56 receiving an arm shaft (not shown) for driving a needle 57 and a thread take-up lever 58 (FIG. 1). The arm shaft carries a handwheel 59 installed with a pulley 60 for the aforesaid belt 19 (FIG. 2). The bracket arm 56 is connected with a standard 61 mounted on a bed 62, in which a shaft 63 is pivoted. The shaft 63 has a pulley 64 and is driven via a timing belt 65 by means of the non-illustrated arm shaft. Furthermore, the shaft 63 is coupled by means of a coupling 66 to a horizontal shaft 67 pivoted in a housing 68 of a saddle 69 (FIG. 3). Concentrically to the horizontal shaft 67 a cylindrical stud 70 having a flange 71, is fastened to the housing 68 by screws 72. The stud 70 is pivoted in bushings 73 arranged in a bracket 74 fastened by screws 75 and 76 to the bed 62 (FIGS. 4,6 and 7). The horizontal shaft 67 ends in an axial bore 77 of a shaft 78 and is fastened by a set screw 79 (FIG. 4). The shaft 78 has a spiral gear 86 and is pivoted in the saddle 69 by a ball bearing 80 arranged in the housing 68 and a needle bearing 81 received in the cylindrical stud 70. According to FIG. 5 a vertical shaft 82 carrying a rotary looptaker 83 is provided with a spiral gear 85 cooperating with the spiral gear 86 and is journaled in bearings 84 received in the saddle 69. Journaled in the rotary looptaker 83 is a bobbin case 87, in which a bobbin 88 with a thread supply 89 is received (FIG. 4). The bobbin case 87 is shaped with a radially extending nose 90 entering a stop notch 91 formed in a bridging bar 92, which is fastened by screws 93 to the flange 71 (FIG. 7), in order to prevent the bobbin case 87 from rotation.
For the purpose of positioning the tiltably arranged saddle 69 is installed with a shifting mechanism 94 (FIGS. 4 and 6). On the cylindrical stud 70 there is clamped a lever 95, the free end of which is linked to an intermediate lever 96 by a bolt 97. The other end of the intermediate lever 96 is hingedly connected to one arm 98 of an angle lever 99 by a bolt 100. The angle lever 99 is pivoted on a bolt 101 fastened by a set screw 102 to the bracket 74. The free arm 103 of the angle lever 99 is provided with a handle 104 and a pin 105, on which a tension spring 106 acts. The free end of the tension spring 106 is connected to a pin 107 arranged in the bed 62 (FIG. 7). For limiting the movement of the angle lever 99 the bracket 74 is provided with a pin 108.
Furthermore, the saddle 69 is equipped with an electrical switch 109, which is fastened by means of screws 110 and a bracket 111. The electrical switch 109 has an actuating lever 112, which cooperates with a threaded stud 113 secured to the bed 62 by a lock nut 114 (FIGS. 4 and 5).
Referring to FIG. 8, in a modified shifting mechanism 115 a pneumatic cylinder 116 is hingedly received on a bolt 117 arranged in the bed 62. On the piston rod 118 there is fastened a forked part 119 secured by a lock nut 120. The forked part 119 is linked to an actuating lever 121 by means of a bolt 122, wherein the actuating lever 121 is clamped on the cylindrical stud 70 similar as in the above described shifting mechanism 94 (FIG. 6).
The total construction of the looptaker arrangement may be best seen from FIG. 9. According to this illustration, the drive motion is transferred from the horizontal shaft 67 to the shaft 78, the spiral gear 86 of which cooperates with the spiral gear 85 rotating the vertical shaft 82. As above described, both, the vertical shaft 82 and the shaft 78 are pivoted in the saddle 69 thus preventing disengagement as the saddle 69 is tilted about the common axis of the shafts 67, 78 and the cylindrical stud 70.
Operation of the present invention can be described as follows:
In sewing condition the saddle 69 is kept in a sewing position, as illustrated in FIGS. 5 and 6, by the shifting mechanism 94 respectively 115. In sewing position the rotary looptaker 83 cooperates with the needle 57 in order to perform stitching. As obvious from FIG. 6, the shifting mechanism 94 firmly locks the saddle 69 via the cylindrical stud 70 in sewing position and prevents any undesired tilting movements. The shifting mechanism 94 is kept in the locked position by the tension spring 106.
For the purpose of replenishing the thread supply 89, the operator tilts the saddle 69 into an easily accessible position by pulling the arm 103 of the angle lever 99 by means of the handle 104 (FIG. 7). In order to prevent starting of the sewing device while the saddle 69 still is in the tilted position for thread replenishing purpose, the electrical switch 109 performs a control function for the operator.
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In a sewing device for sewing fabric cuts on workpiece parts, which are moved by means of a workpiece clamping plate relatively to the needle of a sewing machine, a tiltably arranged and easily accessible vertical axis rotary looptaker for allowing replenishment of thread supply.
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BACKGROUND
Lock assemblies are ubiquitous in the downhole drilling and completions industry. One common type of lock assembly involves locking a plug, choke, pressure holding device, tool, etc., in place by radially extending a plurality of dogs into engagement with corresponding features of a radially disposed tubular. In order to accommodate the dogs, windows must be formed in a mandrel or other component of the tubular string, with relatively narrow struts located between each window presenting likely failure points when the string experiences high pressure situations. This results in the need to balance the width of the dogs and the width of the struts, as making either too small can result in failure of the system (e.g., inability of the dogs to lock the string in place and/or fracture of the struts due to heavy loading). In view of these issues and the prevalence of dog type locking systems in the industry, advances and alternatives in the field of lock assemblies are always well received.
BRIEF DESCRIPTION
A lock assembly including a mandrel having one or more windows arranged alternatingly with one or more struts, one or more dogs corresponding to the one or more windows and radially extendable therethrough, and a member operatively arranged for radially extending each of the one or more dogs, each of the one or more dogs operatively coupled between the member and the mandrel when fully radially extended by the member for bypassing loading in the one or more struts during loading of the assembly.
A method of locking an assembly including causing relative movement between an extender member and a mandrel, the mandrel including one or more windows arranged alternatingly with one or more struts, extending one or more dogs with the extender member through the one or more windows due to the relative movement, landing the one or more dogs at a landing feature, and bypassing loading the in the one or more struts during loading of the assembly due to the one or more dogs being operatively coupled between the mandrel and the member.
BRIEF DESCRIPTION OF THE DRAWINGS
The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
FIG. 1 is a cross-sectional view of a lock assembly having dogs in a retracted state;
FIG. 2 is a cross-sectional view of the lock assembly of FIG. 1 with the dogs in an extended state; and
FIG. 3 is an enlarged view of one of the dogs of FIG. 2 showing a radial overlap between the dog and an extender for the dog.
DETAILED DESCRIPTION
A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
Referring now to FIG. 1 , a locking assembly 10 is shown having a mandrel 12 and an extender 14 . The mandrel 12 includes plurality of windows 16 for accommodating a plurality of locking dogs 18 therein, with one dog 18 in each window 16 . The mandrel 12 further includes struts 20 , with one strut 20 located adjacently between each pair of the windows 16 . The mandrel 12 and the extender 14 are, for example, part of a tubular string runnable downhole in a borehole.
The extender 14 is arranged to radially extend dogs 18 , either radially inwardly or outwardly, through respective ones of the windows 16 . For example, the dogs 18 include a surface 22 that is arranged to correspondingly engage with another surface, e.g., a landing nipple, recess, radial restriction or other engagement surface in a tubular radially disposed with the assembly 10 . For example, the assembly 10 could be run inside of a production tubing string, with the production tubing string including recesses or a landing nipple for receiving the surface 22 of the dogs 18 . For the sake of discussion, a landing nipple 23 of a radially disposed tubular is shown in FIG. 1 (the rest of the tubular including the landing nipple 23 being truncated for clarity of the assembly 10 ). Of course, this is just one example and other arrangements are possible and will be recognized by one of ordinary skill in the art in view of the description of the embodiments herein.
In the illustrated embodiment, the extender 14 includes a plurality of steps (or tiers, ramps, etc.) 24 a - 24 c . Each step 24 a - 24 c is formed as a portion of the extender 14 having a different radial dimension than the other steps for enabling the dogs 18 to progressively extend from the mandrel 12 as the dogs 18 are successively engaged with each step 24 a - 24 c . Any suitable number of steps, ramps or tiers, including just one, could be utilized in other embodiments for extending the dogs 18 to any desired degree. Thus, in the illustrated embodiment, by axially moving the extender 14 with respect to the dogs 18 , the dogs 18 engage successively with each of the ramps 24 a - 24 c , resulting in the dogs 18 extending incrementally further through the windows 16 of the mandrel 12 . The dogs 18 are shown fully retracted in FIG. 1 and fully deployed in FIG. 2 .
In the illustrated embodiment, a threaded connection 26 enables axial movement of the extender 14 with respect to the mandrel 12 , and therefore the dogs 18 , which are held in the windows 16 . Once fully threadingly engaged, a lock mechanism 28 , e.g., a radially compressed ring or c-ring, is arranged to spring outwardly into a corresponding recess 29 for preventing any further relative movement between the extender 14 and the mandrel 12 . Other devices for enabling, and then restricting, relative movement between the mandrel 12 and extender 14 could be used, e.g., a ratcheting device or body lock ring between the mandrel 12 and the extender 14 , etc. It is also to be recognized that non-axial movement of the extender 14 could cause extension of the dogs 18 , e.g., the extender 14 could be a cam (e.g., with ramps of different dimensions arranged circumferentially as opposed to longitudinally) for enabling rotation of the extender 14 to selectively deploy the dogs 18 .
Since the struts 20 are of a narrowed circumferential width (in order to form the windows 16 ), the struts 20 present relatively weak sections of the mandrel 12 that are more likely to fail if the mandrel 12 is subjected to high forces. That is, as the assembly 10 is a locking assembly, it will inevitably be loaded in one or both directions, e.g., by weight of the string with which the assembly 10 is run, pressuring up chambers on either axial side of the assembly, etc.
Accordingly, it is one purpose of the current invention as described herein to avoid loading of, or stress in, the struts 20 during loading of the assembly 10 in or from either axial direction. As discussed above, the extender 14 includes a plurality of ramps 24 a - 24 c . In the illustrated embodiment, the ramps 24 b and 24 c define a set of radial dimensions x 1 and x 2 . The dogs 18 include a surface 30 having a projection 32 therefrom, which respectively share the dimensions x 1 and x 2 when the dogs 18 are engaged with the ramps 24 b and 24 c , and are therefore fully extended by the extender 14 . The radial difference between the two dimensions x 1 and x 2 creates a radial overlap x 3 between the projection 32 of the dogs 18 and the step 24 c of the extender 14 . It is noted that a similar overlap is formed by the step 24 a in order to stabilize the dogs 18 in their run-in positions shown in FIG. 1 .
The overlap x 3 is shown most clearly in FIG. 3 . When the extender 14 becomes fully actuated, e.g., by fully threading the connection 26 between the extender 14 and the mandrel 12 , the step 24 c of the extender 14 will bottom out on the projections 32 of the dogs 18 . In turn, the dogs 18 will bottom out on an edge 34 of the windows 16 of the mandrel 12 . Since movement of the extender 14 is prevented by the lock device 28 , each of the dogs 18 becomes axially locked between the step 24 c of the extender 14 and the edge 34 of each of the windows 16 . Effectively, this makes the dogs 18 a fixed part of the mandrel 12 . In this way, any pressure on the mandrel 12 (e.g., due to a pressure event downhole of the mandrel 12 ) will transfer through the threaded connection 26 to the extender 14 , where it will transfer from the step 24 c of the extender 14 to the projection 32 of the dogs 18 (due to the radial overlap x 3 ), and from the dogs 18 to the landing nipple 23 . In the opposite direction, weight down on the extender 14 will transfer directly through the step 24 c to the dogs 18 to the landing nipple 23 . Advantageously, the radial overlap x 3 enables a bypass of the struts 20 so that they are not stressed during loading (e.g., without the overlap x 3 , the dogs 18 would shift to the edges of the windows 16 opposite from the edges 34 , thereby putting the struts 20 into tension).
While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
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A lock assembly including a mandrel having one or more windows arranged alternatingly with one or more struts. One or more dogs are included corresponding to the one or more windows and are radially extendable therethrough. A member is operatively arranged for radially extending each of the one or more dogs. Each of the one or more dogs is operatively coupled between the member and the mandrel when fully radially extended by the member for bypassing loading in the one or more struts during loading of the assembly.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to fluid distributing devices and more particularly pertains to a garden watering system for surrounding and watering garden plants.
2. Description of the Prior Art
The use of fluid distributing devices is known in the prior art. More specifically, fluid distributing devices heretofore devised and utilized are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
Known prior art fluid distributing devices include U.S. Pat. No. 5,232,159; U.S. Pat. No. 5,168,678; U.S. Pat. No. 4,420,902; U.S. Pat. No. 4,212,134; and U.S. Design Pat. No. 257,064.
While these devices fulfill their respective, particular objectives and requirements, the aforementioned patents do not disclose a garden watering system for surrounding and watering garden plants which includes a guarded spray assembly having a perimeter conduit for positioning about a plant, a water inlet permitting coupling of the perimeter conduit to a water supply line such that pressurized water is sprayed through dispensing apertures onto the surrounded plant, and a plurality of water outlets mounted about the perimeter conduit for permitting fluid coupling of a plurality of the guarded spray assemblies together.
In these respects, the garden watering system according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of surrounding and watering garden plants.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of fluid distributing devices now present in the prior art, the present invention provides a new garden watering system construction wherein the same can be utilized for surrounding and watering garden plants. As such, the general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new garden watering system apparatus and method which has many of the advantages of the fluid distributing devices mentioned heretofore and many novel features that result in a garden watering system which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art fluid distributing devices, either alone or in any combination thereof.
To attain this, the present invention generally comprises a system for surrounding and watering garden plants. The inventive device includes a guarded spray assembly having a perimeter conduit for positioning about a plant. A water inlet permits coupling of the perimeter conduit to a water supply line, whereby pressurized water is sprayed through dispensing apertures onto the surrounded plant. A plurality of water outlets are mounted about the perimeter conduit and permit fluid coupling of a plurality of the guarded spray assemblies together.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
It is therefore an object of the present invention to provide a new garden watering system apparatus and method which has many of the advantages of the fluid distributing devices mentioned heretofore and many novel features that result in a garden watering system which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art fluid distributing devices, either alone or in any combination thereof.
It is another object of the present invention to provide a new garden watering system which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new garden watering system which is of a durable and reliable construction.
An even further object of the present invention is to provide a new garden watering system which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such garden watering systems economically available to the buying public.
Still yet another object of the present invention is to provide a new garden watering system which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Still another object of the present invention is to provide a new garden watering system for surrounding and watering garden plants.
Yet another object of the present invention is to provide a new garden watering system which includes a guarded spray assembly having a perimeter conduit for positioning about a plant, a water inlet permitting coupling of the perimeter conduit to a water supply line such that pressurized water is sprayed through dispensing apertures onto the surrounded plant, and a plurality of water outlets mounted about the perimeter conduit for permitting fluid coupling of a plurality of the guarded spray assemblies together.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is an isometric illustration of a garden watering system according to the present invention in use.
FIG. 2 is an elevation view of the invention, per se.
FIG. 3 is a top plan view thereof.
FIG. 4 is a cross sectional view taken along line 4--4 of FIG. 3.
FIG. 5 is an enlarged cross sectional view of the area set forth in FIG. 4.
FIG. 6 is a cross sectional view taken along line 6--6 of FIG. 3.
FIG. 7 is a cross sectional view taken along line 7--7 of FIG. 3.
FIG. 8 is a top plan view of a plurality of guarded spray means illustrating disparate possible shapes thereof in construction of the present invention 10.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIGS. 1-8 thereof, a new garden watering system embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
More specifically, it will be noted that the garden watering system 10 comprises a guarded spray means 12 for positioning circumferentially about an unillustrated area of ground and a plant situated and growing from such ground for dispensing water from a water supply line 14 onto the plant and surrounding ground. A water inlet means 16 is mounted to the guarded spray means 12 for coupling the guarded spray means to a water supply line 14 as illustrated in FIG. 1 of the drawings. A water outlet means 18 is mounted to the guarded spray means 12 for coupling to a coupling hose 20 which can optionally be utilized to couple to the water inlet means 16 of another guarded spray means 12, whereby a plurality of remotely positioned plants can be watered.
Referring now to FIGS. 2 through 5, it can be shown that the guarded spray means 12 according to the present invention 10 preferably comprises a perimeter conduit 22 of continuous construction. The perimeter conduit, as shown in FIG. 5, is defined by an inner wall 24 spaced from and parallel to an outer wall 26, with an upper wall 28 and a lower wall 30 extending between the inner and outer walls so as to couple the same together in the spaced and parallel orientation and to define an interior spaced through which water or other fluids can flow through the perimeter conduit 22. A plurality of dispensing apertures 32 are directed through the inner wall 24 and into communication with an interior of the perimeter conduit 22 such that a pressurized injection of water into the interior of the perimeter conduit will result in a dispensing of such water through the dispensing apertures 32 towards a center of the perimeter conduit 22, as shown in FIG. 1 of the drawings.
As shown in FIG. 6, the water inlet means 16 according to the present invention 10 preferably comprises an interior threaded fitting 34 mounted to the outer wall 26 of the perimeter conduit 22 and into fluid communication with an interior thereof for permitting threaded coupling with a water supply line 14 such as a garden hose or the like to permit a pressurized injection of water into the perimeter conduit 22. Similarly and as shown in FIG. 7, the water outlet means 18 according to the present invention 10 preferably comprises an exterior threaded fitting 34 mounted to the outer wall 26 of the perimeter conduit 22 and into fluid communication with the interior thereof. A closed cap 38 is normally mounted to the exterior threaded fitting 36 so as to preclude fluid communication therethrough. By this structure, the closed cap 38 can be selectively removed from the exterior threaded fitting 36 to permit the joining of a coupling hose 20 to the water outlet means, whereby such coupling hose 20 can be engaged to the water inlet means 16 of another guarded spray means 12 as shown in FIG. 1 of the drawings.
Referring now to FIG. 8, it can be shown that the perimeter conduit 22 of the guarded spray means 12 is preferably shaped so as to define a circle 40. Alternatively, the perimeter conduit 22 may be shaped so as to define an oval 42 or an oblong oval 44. Further alternative shapes of the perimeter conduit 22 include squares, rectangles, or any other polygonal shape defining a closed loop. It should be further noted that the perimeter conduit 22 need not be continuous or closed in configuration, but yet may be separated along a portion thereof so as to permit lateral positioning of the guarded spray means 12 about a growing plant.
In use, the garden watering system 10 according to the present invention can be easily utilized to effect dispensing of water radially about a plant and the surrounding soil. The present invention 10 can be utilized in a plurality of guarded spray means 12, connected in series or otherwise so as to permit simultaneous watering of a plurality of remote plants. If desired, additional plants can be planted around the invention so as to disguise the same. The present invention may also be constructed of a substantially deformable material and utilized in combination with ground-piercing stakes which extend over an upper edge of the perimeter conduit 22 so as to permit custom forming of the perimeter conduit to a desired shape.
As to a further discussion of the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
with respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
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A system for surrounding and watering garden plants. The inventive device includes a guarded spray assembly having a perimeter conduit for positioning about a plant. A water inlet permits coupling of the perimeter conduit to a water supply line, whereby pressurized water is sprayed through dispensing apertures onto the surrounded plant. A plurality of water outlets are mounted about the perimeter conduit and permit fluid coupling of a plurality of the guarded spray assemblies together.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to porous, polymer particles useful in chromatography and in various analytical, diagnostic techniques and solid state peptide, DNA synthesis, as well as to processes for preparing the same by use of a template polymerization technique.
2. Description of Related Art
Small, uniformly-sized, cross-linked, porous polymer beads find use as a low-cost, stable adsorbent in separating and purifying organic and inorganic materials including polymers and biomolecules. Such beads will also find use in chromatographic separation, filtration, gel permeation, and affinity chromatography. Further use can be contemplated as microcarriers for cell culture in addition to as supports for solid-phase peptide or DNA synthesis. These beads should be chemically compatible to organic solvents over a wide range of pH and should have a desired shape, size, porosity and surface area.
Macroporous bead polymers of cross-linked copolymers which contain functionality are, for example, are described in J. R. Benson and D. J. Woo, J. Chromatographic Sci., 1984, 22, 386. They are prepared by conventional suspension polymerization. First, a monomeric material and cross-linkers are suspended as droplets in an emulsion (water/a water-immiscible organic solvent) with the aid of a surfactant. With the addition of an initiator, polymerization proceeds in the droplets to form gel beads containing the solvent entrapped within the polymeric matrix. The solvent entrapped is removed by extraction with a second solvent such as benzene, toluene, chloroform, etc., leaving macropores in the polymer matrix. On the other hand, the cross-linked polymer phase forms micropores in the matrix. Desired functionality is provided on the surface of the polymers by dervatization thereof. However, when the polymer is derivatized, functional groups are introduced to the polymer surfaces within micropores as well as within macropores. Because of the porous nature of the polymer matrix, the derivatization reaction takes place indiscriminately within any pore structure. Since the functional groups in the microporous region can interact with analytes, chromatographic separation using the polymer beads prepared by the method described above is undesirably influenced by such micropore derivatization. This normally leads to ill-defined peak shapes such as tailing due to different fluid dynamics in the microporous and macroporous regions. When the beads are used as a solid support in a DNA synthesizer, the chain growth of oligonucleotides can occur in the macroporous region as well as in the microporous region. After several steps of chain elongation, the resultant oligonucleotides would be contaminated by unwanted oligomers.
U.S. Pat. No. 5,047,438 to Feibush and Li describes a method of preparing porous polymer particles by polymerizing monomers and cross-linkers in the pores of inorganic template particles and by removing the inorganic template particles without destruction of the polymer structure. In this process, the surface of the polymer structure can further be modified in various ways to impart desired functionality. One such technique involves bonding a monomer carrying desired functionality to the copolymer surface during polymerization, followed by removal of the template material. However, all the techniques disclosed in U.S. Pat. No. 5,047,438 allow the copolymer surface to be modified uniformly. Therefore, the resulting modified (functionalized) polymer particles would, for example, not be suitable for high-resolution chromatography.
Accordingly, a new porous polymer bead which overcome the above problems associated with the prior art polymer particles is definitely needed. This invention addresses such need by providing uniform, macroporous, functionalized polymer particles prepared by a template polymerization technique entirely different from the techniques taught in the prior art.
SUMMARY OF THE INVENTION
It has been discovered that porous polymer particles having desired functionality only in their macroporous region, but not in their microporous region can be prepared by a template polymerization technique in which monomers, cross-linkers, and functional monomers having desired functionality are copolymerized in the presence of a template polymer capable of interacting with the desired functionality and, after polymerization, the template polymer is removed with the result that the desired functional groups are only left in the macroporous region of the polymer matrix.
In one aspect of the invention, there is provided porous, functionalized polymer particles comprising a cross-linked copolymer having microporous regions and macroporous regions in the polymer matrix thereof, wherein the functional groups are essentially present only within the macroporous regions.
In another aspect of the invention, there is provided a method of preparing porous, functionalized polymer particles which comprises the steps of:
(a) providing a polymerizable mixture containing a functional monomer, a cross-linker, and a template polymer, in an aqueous medium to obtain a suspension, the template polymer being capable of forming an ionic or covalent bond with the functional monomer;
(b) copolymerizing the monomer and the cross-linker with or without a polymerization catalyst in the suspension to form a cross-linked copolymer;
(c) removing the aqueous medium and the template polymer from the copolymer to recover porous, functionalized polymer particles, the particles having macroporous regions and microporous regions in the polymer matrix thereof, wherein the functional groups are essentially present only within the macroporous regions.
These features, as well as the nature, scope and utilization of this invention will become readily apparent to one skilled in the art from the following description, the drawings, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphic illustration of the polymer matrix of the polymer bead according to the present invention, where 1 represents a macroporous space, 2 represents a functional group, and 3 represents a cross-linked polymer phase.
FIGS. 2-3 are photomicrographs of macroporous poly(vinyl pyridine/divinylbenzene) beads according to the present invention, with FIG. 1 being taken at ×58.5 and FIG. 2 being taken at ×115.
FIG. 4 is a photomicrograph of the polymer beads shown in FIGS. 2-3 at their surface (taken at ×555).
FIG. 5 is a photomicrograph of fragments or cross-section of the polymer beads shown in FIGS. 2-3 (taken at ×172).
FIG. 6 is a photomicrograph of the bead fragments or cross-section shown in FIG. 5 at a higher magnification (taken at ×780).
DETAILED DESCRIPTION OF THE INVENTION
The present invention is applicable to any copolymers based on monomers carrying desired functionality, additional monomers, and cross-linkers and prepared from the foregoing copolymerizable mixture in the presence of a template polymer in aqueous medium
Suitable monomers carrying desired functionality (herein referred to as "functional monomer") include, but not limited to, monoethylenically unsaturated monomers. Representative of the monomers are vinyl monomers such as vinylpyridine (4-vinylpyridine), vinylphenol (4-vinylphenol), and vinyl-p-toluene-sulfonic acid (4-vinyl-p-toluenesulfonic acid), acrylic acid monomers such as acrylic acid and methacrylic acid, including methacrylic acid halide.
Suitable template polymers include, but not limited to, poly(acrylic acid), poly(vinyl alcohol), and poly(4-vinylpyridine), including poly(4-vinylpyridine-co-styrene).
With proper choice of functional monomers and template polymers, association between both molecules can be accomplished either through an ionic or covalent bonding. For example, when vinylpyridine is employed as the functional monomer, it is preferred to use poly(acrylic acid) as the template polymer. Carboxylic acid moieties in the template polymer ionically interact with pyridiyl groups of the monomer such that monomer molecules align along the backbone structure of the template polymer, as shown in the following scheme: ##STR1##
In the case of monomers with acidic functionalities such as carboxylic acid or sulfonic acid, template polymers carrying basic moieties such as pyridyl can preferably be used. Particularly preferred template polymer is poly(4-vinylpyridine).
Another form of template association is a covalent bonding between the template molecule and the monomers, where functional groups present in the monomer molecule react with reactive groups of the template polymer to form covalent bonds. Representative of such covalent bonds are ester and amide. Thus, where a carboxyl group is desired functionality, acrylic acid halide (or methacrylic acid halide) may be used as the functional monomer. The monomer can be linked to a template polymer having hydroxyl such as polyvinyl alcohol by ester formation, as shown in the following scheme: ##STR2##
Suitable cross-linkers include, but not limited to, divinylbenzene, divinyltoluenes, divinylxylenes, divinylnaphthalenes, divinylethylbenzene, ethylene glycol dimethacrylate, glycidyl methacrylate, pentaerythritol trimethacrylate and the polyvinyl ethers of glycol, glycerol, pentaerythritol and resorcinol. Particularly preferred cross-linkers are polyvinylaromatic hydrocarbons such as divinylbenzene. The cross-linkers are necessary in the present invention, since an uncross-linked polymer may not be strong enough for high-pressure chromatographic use. The cross-linking is also responsible for making the product polymer particles substantially insoluble in any solvents, including strong acidic or alkaline solution.
Apart from the use of functional monomers, additional monomers can be incorporated into a copolymerizable mixture in the present invention. The additional monomers may be hydrophobic and carry other functionality, preferably non-polar. Representative of such monomers are stryrene and the derivatives thereof.
As used herein, the term "macroporous polymers" refers to those having "macropores." In the present context, the "macropore" means pores of average diameter about 3.5 to about 10,000 nm. "Micropore" refers to pores of average diameter from about 0.10 to about 3.5 nm.
The polymer particles of the present invention can be prepared by the aqueous suspension polymerization of a copolymerizable mixture of a monomer, a cross-linker, and, if desired, a second monomer in the presence of a template polymer. In the suspension polymerization procedure, the various ingredients are thoroughly mixed prior to the start of the reaction. While this mixing of the ingredients can be done in a vessel apart from the reaction vessel, for convenience and practical reasons the mixing of the ingredients is normally conducted in the polymerization reaction vessel under an inert atmosphere, particularly where the monomers being employed are subjected to oxidation.
Polymerization proceeds at an elevated temperature, preferably above about 50° C. in the presence or absence of a catalyst. Suitable catalysts that can be used in the present invention include benzoyl peroxide, diacetylperoxide, and azo-bisisobutyronitrile. The amount of catalyst employed is within the range of about 0.005 to about 1.00% by weight, based on the weight of the monomer being polymerized. In the presence of a catalyst, the temperature of reaction is maintained above that at which the catalyst becomes active. Lower temperatures, e.g. about -70° to about 50° C., can be employed if high energy radiation is applied to initiate polymerization. The monomers and the template polymer are diluted in an aqueous medium at a level of from about 5 to about 50% by weight. Suitable aqueous medium comprises water and a water soluble polymer such as poly(vinyl alcohol).
Proper and sufficient agitation or stirring is required throughout the polymerization in order to produce the spherical and porous particles of polymer having the desired size. Thus, the polymerization mixture is agitated to disperse the monomers in the reaction medium by shear action, thereby forming droplets. These droplets should be of such size that when transformed into polymer particles, which are spherical, and porous, the same will be of the desired size. The polymer particles produced in accordance with the present invention preferably have a diameter in the range of about 3 to about 1000 microns. Various means are available to maintain the proper agitation. When polymerization is conducted in a reactor made of stainless steel, such reactor is preferably fitted with a rotatable shaft having one or more agitator blades. When a round-bottom flask is used as a reactor, an overhead stirrer will agitate the reaction medium. The amount of agitation necessary to obtain the desired results will vary depending upon the particular monomers being polymerized, as well as the particular polymer particle size desired. Therefore, the agitation speed such as the rpm (revolutions per minute) must be regulated within certain limits.
Polymerization times varies from about a few hours to a few days, depending on the reactivity of the monomers. After polymerization has proceeded to completion, the polymerization mixture is treated with a water-miscible solvent such as lower alcohol (methanol or ethanol) or acetone. The template polymer used can be removed from the product polymer by extraction with a suitable solvent. For example, if poly(acrylic acid) is the template polymer, it can be extracted into an aqueous alkaline solution. If poly(vinyl)pyridine is employed as the template polymer, aqueous acid solution may be used in the extraction. When the template polymer has formed a covalent bond with the functional monomer, the bond must be cleaved to recover the desired cross-linked polymer. If the covalent bond is an ester or amide linkage, it can be cleaved by alkaline hydrolysis or any other means known to one skilled in the art. Thus, the template polymer may be extracted into a suitable medium such as water, aqueous acid or alkaline solution, depending upon the reactivity of the particular template polymer. After the template polymer has been removed, the product polymer is washed with an appropriate solvent and dried. The dried material is in the form of separate round beads or agglomerates of beads. Agglomerates, if present, are divided into beads mechanically by dispersion in a non-solvent liquid, crushing or grinding.
While the cross-linked polymer phase in the polymer particle forms micropores, the voids which were once occupied by the template polymer molecules and which have resulted from extraction of the template polymer with the appropriate solvent form macropores. Thus, there are two distinctive types of pores of different sizes in the polymer matrix of the polymer particles of the present invention. In order to distinguish between both pore types, the spaces in which the micropores occupy in the polymer matrix are referred to as "microporous regions" and the spaces in which the macropores occupy in the polymer matrix are referred to as "macroporous regions."
After the template polymer molecules have been removed from the polymer matrix and the macroporous regions are formed, the functional groups originating from the functional monomer are populated on the surface of pores in the macroporous regions. By contrast, the microporous regions are substantially free from incorporation of the functional groups. The formation of the microporous and macroporous regions in the polymer matrix is illustrated in FIG. 1.
The functionality to be imparted to the cross-linked copolymer by the method of the present invention is generally polar in nature. A strong acidic group can be incorporated in the copolymer by selecting a monomer having a sulfonic acid group (e.g., 4-vinyl-p-toluenesulfonic acid) and a matching template polymer (e.g., poly(4-vinylpyridine). A weakly acidic group can be incorporated in the copolymer by selecting a monomer having a carboxylic acid and a matching template polymer. Alternatively, a carboxylic acid group can be generated by hydrolyzing a cross-linked acrylic-ester version (as shown in Scheme 2) of the templated polymer particles with a base such as an alkali metal hydroxide solution, to form carboxylic acid groups. Primary or secondary amino groups can be incorporated into the copolymer in a similar manner, providing a weakly basic functionality. If the amino group incorporated is tertiary, this group will be made into a strongly basic moiety by being quarternized with an alkyl halide.
The cross-linked porous polymer particles of the present invention will find an immediate use as an ion exchange resin or adsorbent in chromatography. However, their utility will not be limited to such use. Rather, the particle size, porosity, functionality, and surface area will determine the applications for the polymer beads of the present invention, and these characteristics can be predetermined by selection of the functional monomer, template polymer, and polymerization conditions (particularly agitation speed). Some of the potential uses not indicated herein are polymeric reagents and catalysts. Accordingly, the present invention provides a novel porous polymer particle having a wide variety of industrial uses and an equally novel process of making such polymer particles.
The present invention is illustrated by the following examples. However, it should be understood that the invention is not limited to the details of these examples.
EXAMPLE 1
In this example, the following reagents and solvents were used: Poly(acrylic acid) (PAA) (Aldrich, avg. MW 2,000; 250,000; 3,000,000 and 4,000,000); Divinylbenzene (DVB) (Dow Chem. Company, Midland, Mich.); 4-Vinyl pyridine 4-VPy) (Aldrich, Milwaukee, Wis., b.p. 62°-65° C./15 mm); α,α'-azobisisobutyronitrile (AIBN) (VASO® 67 available from DuPont, Wilmington, Del.); Poly(vinyl alcohol) (PVA) (Aldrich, Milwaukee, Wis., MW 85,000-146,000, 98.99% hydrolyzed); acetone; methanol.
In the actual run, a Brinkman reactor or a round bottom flask equipped with an overhead stirrer was employed. A polymerizable mixture was prepared by admixing one part by mole PAA, one part by mole 4-VPy, one part by mole DVB and 0.5% by weight AIBN based on the total weight of the mixture. The mixture was filtered to remove any insoluble matter and flushed with nitrogen. First, five parts by volume of a 2% PVA aqueous solution was charged to the reactor. Then, one part by volume of the polymerizable mixture was charged to the reactor under stirring while the temperature in the reactor was maintained at 80° C. Reaction continued at 300-900 rpm for 12 hours. The polymerized material was washed with water, acetone and methanol to provide polymer beads. The beads were then extracted successively with acetone, 4N NaOH, and methanol in a Parr reactor under continuous shaking at room temperature for two days. The beads were dried to provide a 90% yield and tested for various physical properties. Under scanning electron microscope (SEM), the beads were determined to be spherical and to have a particle size of between 50 and 300 μm. The mechanical stability of the blades was assessed by packing them in a 150×4.6 mm HPLC column under high pressure. Minimal bead fracture was observed at a pressure up to 3,000 psi. After soaking the beads in 1N HCl and 4N HaOH for several days, there was neither swelling nor chemical degradation detectable by microscopic observation.
These and other results are summarized in Table 1.
TABLE 1______________________________________Pore size: >1 μm (SEM)Pore size distribution: Uniform (SEM)Pore shape: Normal (SEM)Pore volume: 1.9 ml/gApparent density: 0.36 g/mlMechanical stability: ExcellentSwelling resistance: ExcellentChemical stability: ExcellentCross-linking degree: 10-50%______________________________________
A further scanning electron microscope (SEM) study was undertaken to reveal the pore morphology of the polymer beads of the present invention. FIGS. 2-3 clearly show the uniform spherical nature of the beads. FIG. 4 shows that the beads have large pores. The beads were broken to fragments and the fragments were examined for their cross-sectional surfaces under SEM. FIGS. 5-6 show the porous nature of the interior of the beads, where pores and interconnected channels are apparent.
Additionally, a confocal microscope study was undertaken to better understand how the functional groups incorporated are distributed within the polymer matrix of the beads. For a comparison purpose, polymer beads were prepared by polymerizing vinyl pyridine in the presence of polystyrene which does not interact with the monomer. Polystyrene was employed to provide the polymer with pores and channels, and did not fall within the definition of the template polymer as used in the present invention. The thus prepared beads as a control were compared with the beads of the present invention using the confocal microscopy. An objective of this study was to determine how pyridine groups differ from those incorporated in the control beads in the manner in which they are distributed in the beads. In order to locate pyridine groups within the polymer structure of beads, a negatively charged fluorescent dye--Evans Blue--was employed to illuminate pyridine under a confocal microscope. Thus, both the beads of the present invention and the control beads were treated with Evans Blue and examined under a confocal microscope.
A photomicrograph of the control beads shows that blue coloring is spread uniformly in the polymer matrix. This indicates that the pyridine groups are present in the macroporous region as well as in the microporous region with no selective localization in either region.
A photomicrograph of the beads of the present invention shows that blue coloring is confined to pores facing the macroporous region in the polymer. This indicates that the pyridine groups are located only in the macroporous region, not in the microporous region.
These various electron microscopy studies of the polymer beads of the present invention show the porous characteristics of the beads. Moreover, the photographs indicate that functional groups incorporated are essentially present in the macroporous region rather than being present in the microporous region.
The invention now being fully described, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made without department from the spirit or scope of the invention.
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Porous, polymer particles comprising a functionalized cross-linked copolymer having microporous regions and macroporous regions in the polymer matrix thereof, wherein the functional groups are essentially present only within the macroporous regions, as well as processes for preparing these particles based on a template polymerization technique followed by removal of the template polymer from the particles are disclosed. The particles of the invention are useful in chromatography, and in various analytical, diagnostic techniques and solid state peptide, DNA synthesis.
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RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35 U.S.C. §119(e) to co-pending U.S. application Ser. No. 62/069591, filed on Oct. 28, 2014, the contents of which are incorporated by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] The present invention was made with United States government support under Grant No. DE-AR0000326 awarded by the Department of Energy/ARPA-E. The United States government may have certain rights in this invention.
INCORPORATION BY REFERENCE
[0003] All patents, patent applications and publications cited herein are hereby incorporated by reference in their entirety. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art as known to those skilled therein as of the date of the invention described herein.
BACKGROUND
[0004] Phase change (e.g., condensation, vaporization, sublimation, frosting, melting, freezing) occurs on a surface if the surface is cooled or heated below or above the saturation temperature at a given pressure. For example, the condensing phase may grow on the surface as a liquid film and/or as droplets or islands of liquid. Heat transfer through phase change is an important process used in power plant condensers, water harvesters, desalination plants, distillation towers (e.g., hydrocarbons, polyolefins, hydrofluorocarbon, etc.), and thermal/humidity control systems in building. In many applications, it is useful to remove or collect the material after phase change for higher heat transfer efficiency as well as simply collecting the condensates for other use. However, the growth of droplets on condensers to reach the diameter of spontaneous removal is slow due to low rate of vapor diffusion and subsequent droplet coalescence, and the spontaneous shedding of strongly pinned condensates can only happen when the droplets grow to very large sizes. As a result, thick thermally insulating condensate films/droplets persist on low-temperature walls leading to tremendous energy inputs, greenhouse gas emission and excessive usage of coolant. For many industrial applications, it is therefore useful to inhibit or prevent the filmwise buildup of condensing liquid (due to its severe effect on heat transfer) by promoting and accelerating droplet shedding.
[0005] Superhydrophobic surfaces (SHS), which make use of an entrapped air layer to reduce the friction at the solid surface, have been believed to be the most promising technique for higher droplet growth and fast shedding of condensates. Despite more than a decade of intense research, these surfaces are, however, still plagued with inevitable problems: the air layer inhibits heat transfer due to its low thermal conductivity; fully wetted droplets trapped in the structured surface produce highly pinned condensates (or different phase materials, e.g., ice, after phase change); the surfaces get easily contaminated with both organic and inorganic particles; cannot self-heal or self-clean, and are expensive to produce.
[0006] Slippery Liquid-Infused Porous Surfaces or “SLIPS” consist of a film of lubricating liquid locked in place by a nano/microporous substrate. See, FIG. 17 . By proper choice of a lubricant, surface functionalization and nano/microtextured surfaces, the lubricant can be immobilized within the space between and form a conformal overlayer of the nano/micro-asperities producing a slippery liquid interface. The liquid surface is intrinsically smooth and defect-free down to the molecular scale; provides immediate self-repair by wicking into damaged sites in the underlying substrate; and can be chosen to repel immiscible liquids of virtually any surface tension.
[0007] In contrast to superhydrophobic surfaces, SLIPS (or lubricated highly slippery surfaces) have been shown to exhibit negligible contact angle hysteresis when in contact with various condensates, excellent thermal contact due to the absence of the intermediate air layer, and in-plane smooth shedding, particularly over a broad range of temperature and relative humidity or saturation pressure conditions. Previous efforts (Scientific Reports 3, 1988 (2013), and ACS Nano 6, 10122 (2012)) that apply SLIPS to condensation are limited to simple attempts of using SLIPS in humid conditions on flat surfaces.
[0008] Improved or more efficient methods to prevent film buildup and promote droplet shedding are desired.
SUMMARY
[0009] In one aspect, the invention includes introducing nanometer to centimeter scale symmetric and asymmetric, raised or recessed structures onto objects (e.g., metal tubes and fins, polymeric tubes, carbon, cement surfaces, etc.) and applying the SLIPS treatment based on uniform nano/microtextures (“nano/micro-SLIPS”) on such a topographically changed substrate. This creates hierarchically structured SLIPS surfaces.
[0010] In certain embodiments, the topographical features are convex surface structures, that is, the raised structures in which at least a portion exhibits a curved surface having a radius of curvature that is not infinite. In certain embodiments, a portion of the raised topographical features contains curved surfaces. These structures can induce accelerated localized nucleation and growth of condensate.
[0011] In certain embodiments, the topographical features are asymmetric, and the structural anisotropy facilitates fast coalescence and directional shedding of condensate. In one or more embodiments, the raise feature can include an inclined or sloped side that serves as a ‘ramp’ to direct the shedding of the condensate. When combined with the intrinsic ability of nearly friction-free SLIPS surfaces to induce high mobility of droplets, these two geometrical modifications (convexity and anisotropy of additional surface features) collectively enhance the condensation efficiency. Asymmetric and hierarchically structured slippery surfaces (“SLIPS-A”) used in this invention can be applied to a broad range of materials and shapes of surfaces for manufacturing phase change (e.g., condensation, vaporization, sublimation, deposition, melting, freezing)-based devices including heat exchangers, dew harvesting devices, desalination devices, distillation towers (e.g., hydrocarbons, polyolefins, hydrofluorocarbon, etc.), dehumidifiers, evaporation coils, anti-cavitation coatings, vapor deposition devices, etc.
[0012] In one aspect, a phase change-based device includes a thermally conductive substrate having a plurality of raised or recessed macro-features having a convex surface, wherein the macro-features are coated with a slippery coating comprised of a nano- to micro-scale roughened surface and a lubricating liquid stably immobilize in, on and over the roughened surface, wherein the macro-features and the slippery coating, in combination, promotes droplet, solid or bubble formation, growth, and removal of a phase of a phase-change material.
[0013] As used herein the ‘macro-feature’ has a dimension on a scale that is at least 1 order of magnitude, and in some cases 2 orders of magnitude, and in some cases 3 or greater orders of magnitude greater than the nano- to micro-scale roughened surface features. Thus, by way of example, a device according to one or more embodiments, having a raised surface features with dimensions (e.g., height, width and length) on the order of 500 μm-1 mm can have roughened surface with asperities or pores on the order of 200-500 nm (more than a 10 3 -fold difference in dimensions).
[0014] In one aspect, a phase change-based device includes a substrate comprising a plurality of macro-scale raised or recessed features having a convex surface, wherein the geometry of the feature promotes droplet, solid or bubble formation and accelerated growth on the apex of the raised feature, and removal of a phase of a phase-change material.
[0015] In one or more embodiments, the surface with a plurality of macro-scale features is coated with a slippery coating comprised of a lubricating liquid stably immobilize in, on and over the surface to promote accelerated removal of the phase change material.
[0016] In any of the preceding embodiments, the device further includes a slope that transitions from an apex of the raised feature (or nadir of the recessed feature) tangentially to the substrate.
[0017] In any of the preceding embodiments, the raised or recessed features in combination with the slope forms an asymmetric feature to provide directional removal.
[0018] In any of the preceding embodiments, the raised or recessed features in combination with the slope forms a ramp around at least a portion of the raised feature to provide droplet, solid or bubble removal in more than one direction.
[0019] In any of the preceding embodiments, the raised features include at least one rounded edge.
[0020] In any of the preceding embodiments, the raised features include a plateau integral with at least one rounded edge.
[0021] In any of the preceding embodiments, the plateau spans a pair of edges of the raised features.
[0022] In any of the preceding embodiments, the plateau is on the order of 100 nm to 10 cm.
[0023] In any of the preceding embodiments, the raised features include a cone, a hemisphere, a hemi-ellipse, a hemicylinder, pyramids, or bumps of irregular shape.
[0024] In any of the preceding embodiments, the raised features include a flat upper surface and are selected from the group consisting of one or more of cubes, rectangular prisms, cylindrical columns, truncated cones, truncated pyramids and or truncated bumps of irregular shapes.
[0025] In any of the preceding embodiments, the width of the slope increases from the point distal to the substrate to the substrate surface.
[0026] In any of the preceding embodiments, the recessed features is a groove.
[0027] In any of the preceding embodiments, the groove tapers from a first wide width to a second narrow width.
[0028] In any of the preceding embodiments, the groove has an inclined floor that slopes upward tangentially to the substrate surface.
[0029] In any of the preceding embodiments, the groove is in fluid contact with a reservoir holding lubricating liquid.
[0030] The In any of the preceding embodiments, the grooves are arranged to form a plurality of intersecting channels on the substrate.
[0031] In any of the preceding embodiments, the features have a width in the range of 100 nm to 10 cm, or the features are on the order of 0.1 mm to 1 cm.
[0032] In any of the preceding embodiments, the surfaces of the substrate and the macro-scale features comprise a nano-scale to micro-scale roughened surface.
[0033] In any of the preceding embodiments, the roughened surface comprises asperities, texture or porosity in the range of 5 nm to 100 μm, or the roughened surface comprises asperities, texture or porosity in the range of 10 nm to 5 μm.
[0034] In any of the preceding embodiments, the roughened surface is integral with the feature surface.
[0035] In any of the preceding embodiments, the roughened surface is coated over the feature surface.
[0036] In any of the preceding embodiments, the roughened surface is a porous metal oxide.
[0037] In any of the preceding embodiments, the macro-scale features have a roughness of R=0, that is, essentially flat.
[0038] In any of the preceding embodiments. The device of claim 26 , wherein the surface of the device and the features are made of a polymer that can be swollen with the lubricating liquid.
[0039] In any of the preceding embodiments, the surface of the device is chemically functionalized to render surface compatible with the lubricating liquid.
[0040] In any of the preceding embodiments, the lubricating liquid is a hydrophobic or omniphobic liquid.
[0041] In any of the preceding embodiments, the lubricating liquid is selected from the group of hydrocarbon oils, partially or fully fluorinated oils, food-grade oils, mineral oils, silicone oils or ionic liquids.
[0042] In any of the preceding embodiments, the features are made of the same material as the substrate.
[0043] In any of the preceding embodiments, the features and the substrate are made of different materials.
[0044] In any of the preceding embodiments, the features are part of a film attached to the substrate.
[0045] In any of the preceding embodiments, the features are arranged in an array.
[0046] In any of the preceding embodiments, are arranged in an array of rows, and for example, rows of the array are staggered.
[0047] In any of the preceding embodiments, the features are arranged randomly on the surface.
[0048] In any of the preceding embodiments, the features are the same or different in shape, size, steepness of the slope, shape of the slope and direction of the slope.
[0049] In any of the preceding embodiments, the substrate is thermally conductive, and for example, the thermally conductive material includes a metal or the thermally conductive material comprises a metal mesh embedded in a polymer substrate.
[0050] In any of the preceding embodiments, the substrate with raised features is made of a deformable material.
[0051] In any of the preceding embodiments, the device can be reversibly deformed to switch, induce and additionally guide the droplet growth and removal.
[0052] In any of the preceding embodiments, the device is in the shape of a pipe or coil.
[0053] In any of the preceding embodiments, the device further includes a reservoir for supplying lubricating liquid to the device.
[0054] The device further includes microchannels that are aligned and perpendicular to the axis of the pipe to facilitate transport of lubricating liquid from a reservoir through the microchannels.
[0055] In any of the preceding embodiments, the features possess a radius of curvature R bump of hemispherical features (or the width of asymmetric features W) and a feature to feature spacing P pattern and the features are positioned to provide a P pattern /R bump (or P pattern /W) in the range of 1.1 to 100, or P/R is in the range of 2.5-100.
[0056] In any of the preceding embodiments, the device further includes a heat sink or coolant for removing adsorbed heat from the device.
[0057] In any of the preceding embodiments, the device forms at least a portion of a phase change-based device in thermal power plant condensers, water harvesters, desalination plants, distillation towers (e.g., water, hydrocarbons, polyolefins, hydrofluorocarbons), building thermal/humidity, HVAC control systems, or vapor deposition systems.
[0058] In any preceding embodiment, the polymeric film bearing the raised features and infused with the lubricant has channels within the film that carry lubricating liquid. The polymeric film has inside it or at the surface attached to the substrate an artificial self-replenishing vascularized network of channels that provide a reservoir of the liquid transported inside the film.
[0059] In another aspect, the device as described herein is used as thermal power plant condensers, water harvesters, desalination plants, distillation towers (e.g., hydrocarbons, polyolefins, hydrofluorocarbons), building thermal/humidity control systems, or vapor deposition systems.
[0060] In another aspect, a method of condensing a phase change material on surface is provided including providing a phase-change device as described herein, and exposing the heat exchanger to a form of a phase change material wherein the phase change material undergoes a phase change and heat is released or absorbed.
[0061] In any of the preceding embodiments, the phase change material condenses as a droplet on the device.
[0062] In any of the preceding embodiments, the droplets are directionally guided to shed in a predetermined direction.
[0063] In any of the preceding embodiments, the droplets are directionally guided to shed along the direction determined by the widening slope of the asymmetric feature.
[0064] In any of the preceding embodiments, shedding direction is not determined by the orientation of the bump relative to gravity.
[0065] In any of the preceding embodiments, the a thermally conductive substrate is in the form of a pipe or coil.
[0066] In any of the preceding embodiments, the phase change material is water, polyolefins, hydrocarbons, propane, butane, ethylene, ethane, nitrous oxide, sulfur hexafluoride, dimethyl ether, halons, ammonia, sulfur dioxide, fluorocarbons, perfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, bromochlorofluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluoroolefins, brines, eurammon, azeotropic compound, and refrigerants.
[0067] In any of the preceding embodiments, the phase change material is a refrigerant and the material can be one or more of 1,1,1,2,2,3,3,4,4-Nonafluorobutane, Carbon tetrachloride (Tetrachloromethane), Trichlorofluoromethane, Dichlorodifluoromethane, Bromochlorodifluoromethane, Dibromodifluoromethane, Chlorotrifluoromethane, Bromotrifluoromethane, Tetrafluoromethane, Chloroform (Trichloromethane), Dichlorofluoromethane, Chlorodifluoromethane, Bromodifluoromethane, Trifluoromethane (Fluoroform), Dichloromethane (Methylene chloride), Chlorofluoromethane, Difluoromethane, Chloromethane, Fluoromethane, Methane, Hexachloroethane, Pentachlorofluoroethane, 1,1,2,2-Tetrachloro-1,2-difluoroethane, 1,1,1,2-Tetrachloro-2,2-difluoroethane, 1,1,2-Trichlorotrifluoroethane, 1,1,2-Trichlorotrifluoroethane, 1,2-Dichlorotetrafluoroethane, 1,1-Dichlorotetrafluoroethane, 1,2-Dibromotetrafluoroethane, Chloropentafluoroethane, Hexafluoroethane, Pentachloroethane, 1,1,2,2-Tetrachloro-1-fluoroethane, 1,1,1,2-Tetrachloro-2-fluoroethane, 1,1,2-Trichloro-2,2-difluoroethane, 1,1,2-Trichloro-1,2-difluoroethane, 1,1,1-Trichloro-2,2-difluoroethane, 2,2-Dichloro-1,1,1-trifluoroethane, 1,2-Dichloro-1,1,2-trifluoroethane, 1,1-Dichloro-1,2,2-trifluoroethane, 2-Chloro-1,1,1,2-tetrafluoroethane, 1-Chloro-1,1,2,2-tetrafluoroethane, Pentafluoroethane, Pentafluorodimethyl ether, 1,1,2,2-Tetrachloroethane, 1,1,1,2-Tetrachloroethane, 1,1,2-Trichloro-2-fluoroethane, 1,1,2-Trichloro-1-fluoroethane, 1,1,1-Trichloro-2-fluoroethane, Dichlorodifluoroethane, 1,1-Dichloro-2,2-difluoroethane, 1,2-Dichloro-1,1-difluoroethane, 1,1-Dichloro-1,2-difluoroethane, 1,2-Dibromo-1,1-difluoroethane, 1-Chloro-1,2,2-Trifluoroethane, 1-Chloro-2,2,2-Trifluoroethane, 1-Chloro-1,1,2-Trifluoroethane, 1,1,2,2-Tetrafluoroethane, 1,1,1,2-Tetrafluoroethane, Bis(difluoromethyl)ether, 1,1,2-Trichloroethane, 1,1,1-Trichloroethane (Methyl chloroform), 1,2-Dichloro-1-fluoroethane, 1,2-Dibromo-1-fluoroethane, 1,1-Dichloro-2-fluoroethane, 1,1-Dichloro-1-fluoroethane, Chlorodifluoroethane, 1-Chloro-1,2-difluoroethane, 1-Chloro-1,1-difluoroethane, 1,1,2-Trifluoroethane, 1,1,1-Trifluoroethane, Methyl trifluoromethyl ether, 2,2,2-Trifluoroethyl methyl ether, 1,2-Dichloroethane 1,1-Dichloroethane Chlorofluoroethane, 1-Chloro-1-fluoroethane 1,2-Difluoroethane, 1,1-Difluoroethane Chloroethane (ethyl chloride) Fluoroethane Ethane Dimethyl ether, 1,1,1,2,2,3,3-Heptachloro-3-fluoropropane, Hexachlorodifluoropropane 1,1,1,3,3-Pentachloro-2,2,3-trifluoropropane, 1,2,2,3-Tetrachloro-1,1,3,3-tetrafluoropropane, 1,1,1-Trichloro-2,2,3,3,3-pentafluoropropane, 1,2-Dichloro-1,1,2,3,3,3-hexafluoropropane, 1,3-Dichloro-1,1,2,2,3,3-hexafluoropropane, 1-Chloro-1,1,2,2,3,3,3-heptafluoropropane, 2-Chloro-1,1,1,2,3,3,3-heptafluoropropane, Octafluoropropane , 1,1,1,2,2,3-Hexachloro-3-fluoropropane, Pentachlorodifluoropropane, 1,1,1,3,3-Pentachloro-2,2-difluoropropane, Tetrachlorotrifluoropropane, 1,1,3,3-Tetrachloro-1,2,2-trifluoropropane, 1,1,1,3-Tetrachloro-2,2,3-trifluoropropane, Trichlorotetrafluoropropane, 1,3,3-Trichloro-1,1,2,2-tetrafluoropropane, 1,1,3-Trichloro-1,2,2,3-tetrafluoropropane, 1,1,1-Trichloro-2,2,3,3-Dichloropentafluoropropane, 2,2-Dichloro-1,1,1,3,3-pentafluoropropane, 2,3-Dichloro-1,1,1,2,3-pentafluoropropane, 1,2-Dichloro-1,1,2,3,3-pentafluoropropane, 3,3-Dichloro-1,1,1,2,2-pentafluoropropane, 1,3-Dichloro-1,1,2,2,3-pentafluoropropane, 1,1-Dichloro-1,2,2,3,3-pentafluoropropane, 1,2-Dichloro-1,1,3,3,3-pentafluoropropane, 1,3-Dichloro-1,1,2,3,3-pentafluoropropane, 1,1-Dichloro-1,2,3,3,3-pentafluoropropane, Chlorohexafluoropropane, 2-Chloro-1,1,1,2,3,3-hexafluoropropane, 3-Chloro-1,1,1,2,2,3-hexafluoropropane, 1-Chloro-1,1,2,2,3,3-hexafluoropropane, 2-Chloro-1,1,1,3,3,3-hexafluoropropane, 1-Chloro-1,1,2,3,3,3-hexafluoropropane, 1,1,2,2,3,3,3-Heptafluoropropane, Trifluoromethyl 1,1,2,2-tetrafluoroethyl ether, 1,1,1,2,3,3,3-Heptafluoropropane, Trifluoromethyl 1,2,2,2-tetrafluoroethyl ether, Pentachlorofluoropropane, Tetrachlorodifluoropropane, 1,1,3,3-Tetrachloro-2,2-difluoropropane, 1,1,1,3-Tetrachloro-2,2-difluoropropane, Trichlorotrifluoropropane, 1,1,3-Trichloro-2,2,3-trifluoropropane, 1,1,3-Trichloro-1,2,2-trifluoropropane, 1,1,1-Trichloro-2,2,3-trifluoropropane, Dichlorotetrafluoropropane, 2,2-Dichloro-1,1,3,3-tetrafluoropropane, ,2-Dichloro-1,1,1,3-tetrafluoropropane, 1,2-Dichloro-1,2,3,3-tetrafluoropropane, 2,3-Dichloro-1,1,1,2-tetrafluoropropane, 1,2-Dichloro-1,1,2,3-tetrafluoropropane-3-Dichloro-1,2,2,3-tetrafluoropropane, 1,1-Dichloro-2,2,3,3-tetrafluoropropane, 1,3-Dichloro-1,1,2,2-tetrafluoropropane, 1,1-Dichloro-1,2,2,3-tetrafluoropropane, 2,3-Dichloro-1,1,1,3-tetrafluoropropane, 1,3-Dichloro-1,1,3,3-tetrafluoropropane-1-Dichloro-1,3,3,3-tetrafluoropropane, Chloropentafluoropropane, 1-Chloro-1,2,2,3,3-pentafluoropropane, 3-Chloro-1,1,1,2,3-pentafluoropropane, 1-Chloro-1,1,2,2,3-pentafluoropropane, 2-Chloro-1,1,1,3,3-pentafluoropropane, 1-Chloro-1,1,3,3,3-pentafluoropropane, 1,1,1,2,2,3-Hexafluoropropane, 1,1,1,2,3,3-Hexafluoropropane, 1,1,1,3,3,3-Hexafluoropropane, 1,2,2,2-Tetrafluoroethyl difluoromethyl ether, Hexafluoropropane, Tetrachlorofluoropropane, Trichlorodifluoropropane, ichlorotrifluoropropane, 1,3-Dichloro-1,2,2-trifluoropropane, 1,1-Dichloro-2,2,3-trifluoropropane, 1,1-Dichloro-1,2,2-trifluoropropane, 2,3-Dichloro-1,1,1-trifluoropropane, 1,3-Dichloro-1,2,3-trifluoropropane, 1,3-Dichloro-1,1,2-trifluoropropane, Chlorotetrafluoropropane, 2-Chloro-1,2,3,3-tetrafluoropropane, 2-Chloro-1,1,1,2-tetrafluoropropane, 3-Chloro-1,1,2,2-tetrafluoropropane, 1-Chloro-1,2,2,3-tetrafluoropropane, 1-Chloro-1,1,2,2-tetrafluoropropane, 2-Chloro-1,1,3,3-tetrafluoropropane, 2-Chloro-1,1,1,3-tetrafluoropropane, 3-Chloro-1,1,2,3-tetrafluoropropane, 3-Chloro-1,1,1,2-tetrafluoropropane, 1-Chloro-1,1,2,3-tetrafluoropropane, 3-Chloro-1,1,1,3-tetrafluoropropane, 1-Chloro-1,1,3,3-tetrafluoropropane, 1,1,2,2,3-Pentafluoropropane, Pentafluoropropane, 1,1,2,3,3-Pentafluoropropane, 1,1,1,2,3-Pentafluoropropane, 1,1,1,3,3-Pentafluoropropane, Methyl pentafluoroethyl ether, Difluoromethyl 2,2,2-trifluoroethyl ether, Difluoromethyl 1,1,2-trifluoroethyl ether, Trichlorofluoropropane, Dichlorodifluoropropane, 1,3-Dichloro-2,2-difluoropropane, 1,1-Dichloro-2,2-difluoropropane, 1,2-Dichloro-1,1-difluoropropane, 1,1-Dichloro-1,2-difluoropropane, Chlorotrifluoropropane, 2-Chloro-1,2,3-trifluoropropane, 2-Chloro-1,1,2-trifluoropropane, 1-Chloro-2,2,3-trifluoropropane, 1-Chloro-1,2,2-trifluoropropane, 3-Chloro-1,1,2-trifluoropropane, 1-Chloro-1,2,3-trifluoropropane, 1-Chloro-1,1,2-trifluoropropane, 3-Chloro-1,3,3-trifluoropropane, 3-Chloro-1,1,1-trifluoropropane, 1-Chloro-1,1,3-trifluoropropane, 1,1,2,2-Tetrafluoropropane, ethyl 1,1,2,2-tetrafluoroethyl ether, Dichlorofluoropropane, 1,2-Dichloro-2-fluoropropane, Chlorodifluoropropane, 1-Chloro-2,2-difluoropropane, 3-Chloro-1,1-difluoropropane , 1-Chloro-1,3-difluoropropane, Trifluoropropane , Chlorofluoropropane, 2-Chloro-2-fluoropropane, 2-Chloro-1-fluoropropane, 1-Chloro-1-fluoropropane, Difluoropropane, Fluoropropane, Propane, Dichlorohexafluorocyclobutane , Chloroheptafluorocyclobutane, Octafluorocyclobutane, (Perfluorocyclobutane), Decafluorobutane (Perfluorobutane), 1,1,1,2,2,3,3,4,4-Nonafluorobutane, 1,1,1,2,3,4,4,4-Octafluorobutane, 1,1,1,2,2,3,3-Heptafluorobutane, Perfluoropropyl methyl ether, Perfluoroisopropyl methyl ether, 1,1,1,3,3-Pentafluorobutane, Dodecafluoropentane (Perfluoropentane) , or Tetradecafluorohexane (Perfluorohexane).
[0068] In any of the preceding embodiments, the phase change material forms as a liquid (droplet), gas (bubble) or solid.
[0069] In any of the preceding embodiments, the solid is a particle in any shape or clusters of particles in any shape, or the phase change material is water, or the feature height is less than the depletion layer, or the features have a width on the dimension of the condensing droplets.
[0070] In any of the preceding embodiments, the asymmetric structures have a width that is the same as the diameter of the shedding droplets
[0071] In any of the preceding embodiments, the phase change device is a heat exchanger and further comprising transferring heat released or absorbed by the latent heat exchanger using a heat sink in thermal contact with the heat exchanger.
[0072] In any of the preceding embodiments, the heat exchanger is functional to effect condensation in multi-stage flash (MSF) desalination plants, thermal and humidity management systems for buildings, etc., liquid harvesting by facilitating the condensation of vapor, effective prevention of mechanical failure of underwater ship parts (e.g., motor screws) by the relief of impact of bubbles generated from cavitation, release of bubbles that hinder the transport of liquid in the pipe and release of inorganic and organic fouling.
[0073] In another aspect, a method of decoupling phase change material growth and transport includes providing a phase change-based device a deformable substrate comprising a plurality of macro-scale raised features having a convex surface, wherein the geometry of the feature promotes droplet, solid or bubble formation and accelerated growth on the apex of the raised feature; and condensing a phase change material on at last the apices of the macro-scale raised features or the device; and deforming the substrate and the macro-scale raised features to remove a phase of a phase-change material from the apices.
[0074] Convexity, or raised topography in a broader sense, can also contribute to faster droplet formation due to the focusing effect of diffusion flux of the incoming phase before phase change on the convex surface texture. In one or more embodiments, the SLIPS-based heat exchanger surfaces demonstrate “convexity effects” that nucleate large droplets and bubbles in shorter time scales compared to state-of-the-art superhydrophobic or traditional SLIPS-treated surfaces, and significantly shorter times compared to regular, untreated condenser materials. In one or more embodiments, a latent heat exchanger or condenser contains nanometer to centimeter scale convex surface structures that are treated with a SLIPS surface; the device shows several times faster droplet growth and shedding compared to superhydrophobic or traditional SLIPS-treated surfaces, and significantly faster times compared to regular, untreated condenser materials.
[0075] The individually described embodiments of the claim may be used in the alternative and in combination with any other embodiments described within.
[0076] These and other aspects and embodiments of the disclosure are illustrated and described below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0077] The invention is described with reference to the following figures, which are presented for the purpose of illustration only and are not intended to be limiting.
[0078] In the Drawings:
[0079] FIG. 1A-1B are schematic illustrations of exemplary convex structures that be used for droplet, bubble or particle nucleation and growth according to one or more embodiments; FIG. 1A (i)-(iii) illustrates a series of surfaces including (i) symmetrical convex features, (ii) asymmetrical convex features containing a single slope for directional transport and (iii) asymmetric and symmetric convex features containing slopes in multiple directions for multidirectional transport; and FIG. 1B (i)-(iii) illustrates similar features that further contain a SLIPS coating.
[0080] FIG. 2A is an optical profilometer image of an exemplary convex structure that can be used for the SLIPS-based heat exchanger surfaces, according to one or more embodiments.
[0081] FIG. 2B shows SEM (top) and contact profilometer (bottom) images of spherical-cap-shaped bumps without PDMS coating (i.e., aluminum, left images) as well as SEM and contact profilometer images of spherical-cap-shaped bumps with PDMS coating (right images)
[0082] FIG. 2C shows a profilometer image of a hexagonal array of millimeter-scale spherical-cap-shaped bumps (left), and the location of the plane below which diffusion is the dominant mechanism of mass transport (depletion layer δ>>H, dotted line, right).
[0083] FIG. 2D shows time-lapsed images of droplets growing by condensation on the apex of the bumps (top row) compared to a flat region with the same height H (bottom row). The largest droplet in each series is denoted by dotted circles at each time point.
[0084] FIG. 2E shows that (left) the spherical-cap-shaped bump without additional roughening by sandpaper exhibits larger droplets on its apex compared to those of (right) the roughened flat surfaces of the square-shaped bump with the same height, thus ruling out the importance of the micro/nano surface roughness to the observed preferential droplet growth at the apex of the structures.
[0085] FIG. 2F shows three different schematic illustrations for deriving a simple scaling law to describe the effect of radius of curvature on diffusion flux (J C ) focused on the apex of spherical-cap-shaped bumps: (left) Schematic illustration (cross-sectional view) of depletion layer (represented by dotted line) and a spherical-cap-shaped bumped surface (represented by solid line), in which the rectangle and point represent the area and point of interest, respectively; (center) a spherical mass sink corresponding to the spherical-cap-shaped bump; and (right) the spherical mass sink and its mirror image (a corresponding spherical mass source represented by dotted line) used to calculate the concentration distribution and gradient near the point of interest.
[0086] FIG. 2G is a plot based on an analytical model that predicts magnitude of diffusion flux (J C ) on the apex of a spherical bump as a function of the radius of curvature (κ −1 ). Values are normalized to diffusion flux on flat surfaces with the same H.
[0087] FIG. 2H shows time-dependent droplet growth on bumps with decreasing radii of curvature at the apex. 2r max is the averaged diameter of the three largest droplets found on the apex of the bumps.
[0088] FIGS. 3A-3B are illustrations of an edge-containing structure design according to one or more embodiments.
[0089] FIG. 3C is a schematic illustration of various raised features according to one or more embodiments.
[0090] FIG. 3D is an optical image of condensed droplets on rectangular bumps with the same height but different widths.
[0091] FIG. 3E shows time-dependent droplet growth on bumps with different width. Droplets on the rectangular bump with the smallest width can grow for a longer time at a constant growth rate, leading to a greater droplet size compared to spherical-cap-shaped bumps at later time points.
[0092] FIG. 4A shows droplet transport directions on a rectangular bump;
[0093] FIG. 4B shows droplet transportation a bump modified with an asymmetric slope.
[0094] FIG. 4C shows energy profile normalized by the difference between the maximum and minimum value of total free energy of the asymmetric bump-droplet-vapor system, obtained by finite element-based numerical calculation (Surface Evolver).
[0095] FIG. 4D is a profilometer image (oblique view) of a friction-free asymmetric bump according to one or more embodiments, showing nanostructure that is infused with lubricant to create a molecularly smooth slippery coating, and the tangentially connected bottom slope used to prevent pinning
[0096] FIG. 4E (i)-(iv) are schematic illustrations of various raised features containing a slope tangentially transitioning from the apex of the feature to the surface according to one or more embodiments.
[0097] FIG. 4F shows time-lapsed optical images of condensed water droplets on an asymmetric bump rotated 180° relative to gravity and showing that while on the bump, the droplet is moving against gravity in the direction determined by the orientation of the slope.
[0098] FIG. 4G shows time-lapsed optical images of condensed water droplets on an exemplary asymmetric structure in combination with the SLIPS coating rotated 90° relative to gravity showing that the droplet travels solely in the direction determined by the bump geometry until it reaches the end of the bump and makes an immediate 90° turn to align with gravity. The dotted line tracks the horizontal motion of the droplet on the bump.
[0099] FIG. 4H is a series of time-elapsed photographs of an exemplary asymmetric structure in combination with the SLIPS coating (i.e., SLIPS-A) (i)-(iii), showing more than 20-fold reduced time for the first shedding droplet compared to superhydrophobic surfaces (iv) and SHS-A (i.e., a superhydrophobic surface with asymmetric features) (v) due to the topographically-preferential condensation induced by a convex structure, forced coalescence and directional transport induced by the asymmetry of the design, and fast droplet movement induced by the negligible friction on SLIPS-A.
[0100] FIG. 41 shows quantitative analysis of growth dynamics and shedding for slippery asymmetric bumps (▴), superhydrophobic asymmetric bumps (Δ), flat slippery control (▪) and superhydrophobic (□) control. Each data point represents the averaged value of the largest droplet's growth on each of three different bumps or locations in the case of flat surfaces. Both slippery asymmetric bumps (▴) and superhydrophobic asymmetric bumps (Δ) show faster localized droplet growth in the early stage (t<10 3 sec) compared to flat slippery (▪) and superhydrophobic (□) controls. Drops on slippery asymmetric bumps exhibit a further enhanced growth rate (rectangular box in the middle of the plot) as they move down the bump slope, approximately six-fold greater than typical droplet growth dynamics, and the shortest t first (i.e., the average time at which the first three drops are transported solely by gravity) of <˜20 min. Each data point in the red box represents the averaged size of these three drops. Inset shows a magnified view of the fast growth, attributed to positive feedback between coalescence-driven growth and capillary transport. Neither superhydrophobic asymmetric bumps nor flat superhydrophobic surfaces produce shedding droplets within t˜200 min.
[0101] FIG. 4J is a plot of droplet diameter over time showing fast growth and transport of droplets on slippery asymmetric bumps compared to bottom edge regions. Each data point outside the three circles represents the average size of at least the three largest droplets on each surface. Each data point inside the three circles represents the diameter of the largest droplet on each of the bumps, obtained by tracking the same droplet on each of three different bumps.
[0102] FIG. 4K shows droplet condensation for an exemplary array of the slippery asymmetric bumps (left) compared to the flat slippery surfaces (right).
[0103] FIG. 4L shows a plot of collected water for the array of the slippery asymmetric bumps (▴) and flat slippery surfaces (▪), demonstrating that an exemplary array of the slippery asymmetric bumps (triangle in the plot) shows a significantly greater volume of water collected at the bottom of the surface, compared to the flat slippery surfaces (square in the plot).
[0104] FIG. 4M shows steady state water collection performance on bumpy (▴) and flat (▪) slippery surfaces.
[0105] FIG. 4N shows droplet growth curve on four representative types of surfaces—macroscopic asymmetric bumps with nanostructure (without lubricant, Δ, slope=0.62, SHS-A), macroscopic asymmetric bumps with molecularly smooth lubricant (▴, slope=0.78, SLIPS-A), flat slippery coatings (without macroscopic bump, ▪, slope=0.79, SLIPS), and flat superhydrophobic surfaces (as a control, ◯, slope=0.86, SHS).
[0106] FIG. 4O and FIG. 4P show images of droplets condensed on slippery ( FIG. 4O ) spherical-cap-shaped bumps and ( FIG. 4P ) rectangular bumps. Even with slippery coatings, the bumps used in FIG. 2H and FIG. 3E did not display shedding droplets even though the droplets are greater than the shedding droplet diameter (denoted by dotted horizontal line) measured on flat surfaces, showing the importance of the asymmetric topography of bumps with the presence of a directional ramp.
[0107] FIG. 5 is an illustration of an exemplary asymmetric structure designs with geometrical parameters according to one or more embodiments.
[0108] FIG. 6 is an image showing the results of computational image analysis of experimental results of shedding droplets on different surfaces, in which the hollow white dotted circles represent the detected droplets and the tails with vertical white dotted lines represent the trace of shedding droplets. The time and diameter of the shedding droplets passing the horizontal black dotted line are recorded using MATLAB codes
[0109] FIG. 7 is a schematic illustration of the overall heat transfer coefficient measurement setup.
[0110] FIG. 8 is a schematic illustration of an exemplary high-throughput manufacturing process with the images of fabricated hierarchical asymmetric structures at different length scales.
[0111] FIG. 9 is a plot of the volume or the droplets shed as a function of time from SLIPS and SLIPS-A surfaces of FIG. 6 .
[0112] FIG. 10 is a plot of overall heat transfer coefficient (OHTC) values normalized by the OHTC value of SHS (OHTC/OHTC SHS ) comparing bare aluminum surface, SHS surface, traditional SLIPS surface and hierarchical SLIPS surface with rationally designed convex and asymmetric features (SLIPS-A).
[0113] FIG. 11 is a schematic cross-sectional illustration of a raised feature according to one or more embodiments, illustrating surface feature parameters R bump (radius of curvature of a convex hemispherical raised feature) P pattern (center to center distance between adjacent ‘bumps’), and H (height of a raised feature), as well as δ (depletion layer thickness below which mass transport (e.g., vapor) is governed by diffusion, according to one or more embodiments.
[0114] FIG. 12A and FIG. 12B are analyses of droplet growth dynamics on both the bumped and the surrounding flat surface, in which FIG. 12A is a time-lapsed sequential images of condensed droplets on the same bump and surrounding; and FIG. 12B is a quantitative analysis of droplet growth with time following the simple model (r˜αt β ).
[0115] FIG. 13 is an infrared camera image (bottom) of the rectangular bump (top, optical camera image), which shows no distinct temperature difference between the top flat area of the rectangular bump and the surrounding basal region. The unit of temperature next to the color bar is in ° C.
[0116] FIG. 14A is an image of water droplets condensed on a conical surface across which a temperature gradient was applied after t=4×10 3 sec; while the left side is kept at a lower temperature than right side, and therefore higher condensation would be expected on that side, the curvature of the tube increases to the right and this effect dominates the temperature effect, resulting in larger droplets formed on the side with smaller pipe radius.
[0117] FIG. 14B shows a family of averaged droplet size (2r avg ) as a function of position. Circle, diamond, square, and triangle represent t=1×10 3 , 2×10 3 , 3×10 3 , and 4×10 3 sec, respectively.
[0118] FIG. 14C is (i) an image of pipes of different diameters with an identical hydrophobic coating (FS-100), illustrating the effect of radius of curvature on droplet size and (ii) a plot of droplet diameter with pipe diameter, showing the effect of the radius of curvature (or diameter) of pipe geometry, another kind of convex curvature geometry widely used for industrial heat exchanger design, on drop growth. As confirmed in SLIPS-A experiments, the smaller the diameter of pipes, the faster the growth of the droplets.
[0119] FIG. 14D is a schematic illustration of a droplet on SLIPS pipe (cross sectional view) Of different diameters, showing the effect of diameter of pipes on the magnitude of driving force (gravitational force's component that is tangential to the pipe surface) of droplet shedding.
[0120] FIG. 14E is a plot of initial volume of shedding droplets (N=10), supporting the additional favorable effect of smaller pipe diameter on shedding droplet volume (or size) leading to earlier transport of droplets.
[0121] FIG. 14F is a plot of resultant water collection on different SLIPS pipes. The combined effects of fast drop growth and transport on a smaller diameter pipe results in a much greater amount of collected water per unit area of pipes.
[0122] FIG. 14G is an exemplary setup of simple lubricant-replenishment system by employing microchannel and oleophilic material.
[0123] FIG. 14H shows an enlarged exemplary combination of microchannels running vertically and horizontally in a surface used to replenish lubricant over time.
[0124] FIG. 14I is an image of a surface including (right) hemicylindrical raised features and (left) hemicylindrical features having periodic raised bumps to create a hierarchical structure according to one or more embodiments.
[0125] FIG. 15A is a schematic illustration of drop movement and coalescence when underlying stretchable substrate is elongated in y-direction for a flat surface and a bumpy surface.
[0126] FIG. 15B is a schematic illustration of the fabrication steps for creating a dynamic harvester.
[0127] FIG. 15C is an image of an exemplary dynamic harvester according to one or more embodiments.
[0128] FIG. 15D shows the results of the condensation experiments using a dynamic harvester. Optical images show the predicted fast drop growth by (unstretched) bumps (i) and the effect of stretching the substrate on further growth by guided coalescence (ii). The plot on the bottom right (iv) shows gradual drop growth in the process of stretching and relaxing represented by strain-time plot (iii).
[0129] FIG. 16A and B represent an ideal Rankine cycle. High temperature steam with high pressure generated from the boiler (Q H , 2 or 2′→3) rotates the turbine (W T , 3→4 or 4′). While rotating the turbine, the saturated steam expands resulting in lower temperature and pressure. It undergoes a phase change from vapor to liquid in the condenser (Q L , 4→ or 4′→1′) by heat exchange with coolants. The condensed water is pumped (W P , 1→2 or 1′→2′) to the boiler and then reused to make this thermodynamic cycle. The abscissa and ordinate are entropy and temperature, respectively.
[0130] FIGS. 17A-17E are schematic representations of various SLIPS surface, showing examples of surfaces with immobilized lubricant overlayer: A) nano/microtextured surfaces with the roughness factor R>1; B) largely flat surfaces that utilize the natural roughness of the material (R=1); C) nano/microtextured surfaces with the roughness factor R>1 with the lubricant conformally coating the nano/micro-asperities; D) nano/microtextured curved surfaces having a positive radius of curvature with the roughness factor R>1 with the lubricant conformally coating the nano/micro-asperities; and E) a nano/micro/millimeter scale flexible solid film layer that can hold and diffuse the lubricating layer.
DETAILED DESCRIPTION
[0131] A simple, scalable, environment-friendly, and low-cost design and fabrication of SLIPS-based phase change-based devices (e.g., condensation, vaporization, sublimation, frosting, melting, freezing) is described. As one example of phase change-based devices, a latent heat exchanger allows energy to be released or absorbed by a body during a constant-temperature process. A typical example is a change of state such as the freezing or boiling of liquid (e.g., water, hydrocarbons, propane, butane, ethylene, ethane, nitrous oxide, sulfur hexafluoride, dimethyl ether, halons, ammonia, sulfur dioxide, fluorocarbons, perfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, silicones, bromochlorofluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluoroolefins, brines, eurammon, azeotropic compound, and compounds of aforementioned refrigerants) or the condensation of vapor (e.g., water, polyolefins, hydrocarbons, propane, butane, ethylene, ethane, nitrous oxide, sulfur hexafluoride, dimethyl ether, halons, ammonia, sulfur dioxide, fluorocarbons, perfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, silicones, bromochlorofluorocarbons, perfluorocarbons, hydrofluorocarbons, hydrofluoroolefins, brines, eurammon, azeotropic compounds, and refrigerants). The heat exchanger surface can be applied on a wide range of metallic surfaces (or any thermal-conductive surface including polymeric surfaces) and can be used in a broad range of heat exchangers to enhance the heat transfer performance in the temperature range from superfreezing to superheating conditions (at which phase changes such as condensation and boiling occur). In illustrating the invention, water is used as a specific example of a system that can undergo condensation and heat exchange. Water is used for the purpose of illustration only and it is contemplated that one can employ the phase change and latent heat absorbers described herein for a range of phase-change fluids, for example to condense phase-change fluids from vapor phase to liquid phase. Exemplary phase-change fluids include water, polyolefins, hydrocarbons, propane, butane, ethylene, ethane, nitrous oxide, sulfur hexafluoride, dimethyl ether, halons, ammonia, sulfur dioxide, fluorocarbons, perfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, bromochlorofluorocarbons, hydrofluoroolefins, silicones, brines, eurammon, azeotropic compound, and compounds of aforementioned refrigerants, or hydrofluorocarbon (such as for example fluorinerts and vertrels), refrigerants such as Carbon tetrachloride (Tetrachloromethane), Trichlorofluoromethane, Dichlorodifluoromethane, Bromochlorodifluoromethane, Dibromodifluoromethane, Chlorotrifluoromethane, Bromotrifluoromethane, Tetrafluoromethane, Chloroform (Trichloromethane), Dichlorofluoromethane, Chlorodifluoromethane, Bromodifluoromethane, Trifluoromethane (Fluoroform), Dichloromethane (Methylene chloride), Chlorofluoromethane, Difluoromethane, Chloromethane, Fluoromethane, Methane, Hexachloroethane, Pentachlorofluoroethane, 1,1,2,2-Tetrachloro-1,2-difluoroethane, 1,1,1,2-Tetrachloro-2,2-difluoroethane, 1,1,2-Trichlorotrifluoroethane, 1,1,2-Trichlorotrifluoroethane, 1,2-Dichlorotetrafluoroethane, 1,1-Dichlorotetrafluoroethane, 1,2-Dibromotetrafluoroethane, Chloropentafluoroethane, Hexafluoroethane, Pentachloroethane, 1,1,2,2-Tetrachloro-1-fluoroethane, 1,1,1,2-Tetrachloro-2-fluoroethane, 1,1,2-Trichloro-2,2-difluoroethane, 1,1,2-Trichloro-1,2-difluoroethane, 1,1,1-Trichloro-2,2-difluoroethane, 2,2-Dichloro-1,1,1-trifluoroethane, 1,2-Dichloro-1,1,2-trifluoroethane, 1,1-Dichloro-1,2,2-trifluoroethane, 2-Chloro-1,1,1,2-tetrafluoroethane, 1-Chloro-1,1,2,2-tetrafluoroethane, Pentafluoroethane, Pentafluorodimethyl ether, 1,1,2,2-Tetrachloroethane, 1,1,1,2-Tetrachloroethane, 1,1,2-Trichloro-2-fluoroethane, 1,1,2-Trichloro-1-fluoroethane, 1,1,1-Trichloro-2-fluoroethane, Dichlorodifluoroethane, 1,1-Dichloro-2,2-difluoroethane, 1,2-Dichloro-1,1-difluoroethane, 1,1-Dichloro-1,2-difluoroethane, 1,2-Dibromo-1,1-difluoroethane, 1-Chloro-1,2,2-Trifluoroethane, 1-Chloro-2,2,2-Trifluoroethane, 1-Chloro-1,1,2-Trifluoroethane, 1,1,2,2-Tetrafluoroethane, 1,1,1,2-Tetrafluoroethane, Bis(difluoromethyl)ether, 1,1,2-Trichloroethane, 1,1,1-Trichloroethane (Methyl chloroform), 1,2-Dichloro-1-fluoroethane, 1,2-Dibromo-1-fluoroethane, 1,1-Dichloro-2-fluoroethane, 1,1-Dichloro-1-fluoroethane, Chlorodifluoroethane, 1-Chloro-1,2-difluoroethane, 1-Chloro-1,1-difluoroethane, 1,1,2-Trifluoroethane, 1,1,1-Trifluoroethane, Methyl trifluoromethyl ether, 2,2,2-Trifluoroethyl methyl ether, 1,2-Dichloroethane 1,1-Dichloroethane Chlorofluoroethane, 1-Chloro-1-fluoroethane 1,2-Difluoroethane, 1,1-Difluoroethane Chloroethane (ethyl chloride) Fluoroethane Ethane Dimethyl ether, 1,1,1,2,2,3,3-Heptachloro-3-fluoropropane, Hexachlorodifluoropropane 1,1,1,3,3-Pentachloro-2,2,3-trifluoropropane, 1,2,2,3-Tetrachloro-1,1,3,3-tetrafluoropropane, 1,1,1-Trichloro-2,2,3,3,3-pentafluoropropane, 1,2-Dichloro-1,1,2,3,3,3-hexafluoropropane, 1,3-Dichloro-1,1,2,2,3,3-hexafluoropropane, 1-Chloro-1,1,2,2,3,3,3-heptafluoropropane, 2-Chloro-1,1,1,2,3,3,3-heptafluoropropane, Octafluoropropane , 1,1,1,2,2,3-Hexachloro-3-fluoropropane, Pentachlorodifluoropropane, 1,1,1,3,3-Pentachloro-2,2-difluoropropane, Tetrachlorotrifluoropropane, 1,1,3,3-Tetrachloro-1,2,2-trifluoropropane, 1,1,1,3-Tetrachloro-2,2,3-trifluoropropane, Trichlorotetrafluoropropane, 1,3,3-Trichloro-1,1,2,2-tetrafluoropropane, 1,1,3-Trichloro-1,2,2,3-tetrafluoropropane, 1,1,1-Trichloro-2,2,3,3-Dichloropentafluoropropane, 2,2-Dichloro-1,1,1,3,3-pentafluoropropane, 2,3-Dichloro-1,1,1,2,3-pentafluoropropane, 1,2-Dichloro-1,1,2,3,3-pentafluoropropane, 3,3-Dichloro-1,1,1,2,2-pentafluoropropane, 1,3-Dichloro-1,1,2,2,3-pentafluoropropane, 1,1-Dichloro-1,2,2,3,3-pentafluoropropane, 1,2-Dichloro-1,1,3,3,3-pentafluoropropane, 1,3-Dichloro-1,1,2,3,3-pentafluoropropane, 1,1-Dichloro-1,2,3,3,3-pentafluoropropane, Chlorohexafluoropropane, 2-Chloro-1,1,1,2,3,3-hexafluoropropane, 3-Chloro-1,1,1,2,2,3-hexafluoropropane, 1-Chloro-1,1,2,2,3,3-hexafluoropropane, 2-Chloro-1,1,1,3,3,3-hexafluoropropane, 1-Chloro-1,1,2,3,3,3-hexafluoropropane, 1,1,2,2,3,3,3-Heptafluoropropane, Trifluoromethyl 1,1,2,2-tetrafluoroethyl ether, 1,1,1,2,3,3,3-Heptafluoropropane, Trifluoromethyl 1,2,2,2-tetrafluoroethyl ether, Pentachlorofluoropropane, Tetrachlorodifluoropropane, 1,1,3,3-Tetrachloro-2,2-difluoropropane, 1,1,1,3-Tetrachloro-2,2-difluoropropane, Trichlorotrifluoropropane, 1,1,3-Trichloro-2,2,3-trifluoropropane, 1,1,3-Trichloro-1,2,2-trifluoropropane, 1,1,1-Trichloro-2,2,3-trifluoropropane, Dichlorotetrafluoropropane, 2,2-Dichloro-1,1,3,3-tetrafluoropropane-2-Dichloro-1,1,1,3-tetrafluoropropane, 1,2-Dichloro-1,2,3,3-tetrafluoropropane, 2,3-Dichloro-1,1,1,2-tetrafluoropropane, 1,2-Dichloro-1,1,2,3-tetrafluoropropane-3-Dichloro-1,2,2,3-tetrafluoropropane, 1,1-Dichloro-2,2,3,3-tetrafluoropropane, 1,3-Dichloro-1,1,2,2-tetrafluoropropane, 1,1-Dichloro-1,2,2,3-tetrafluoropropane, 2,3-Dichloro-1,1,1,3-tetrafluoropropane, 1,3-Dichloro-1,1,3,3-tetrafluoropropane-1-Dichloro-1,3,3,3-tetrafluoropropane, Chloropentafluoropropane, 1-Chloro-1,2,2,3,3-pentafluoropropane, 3-Chloro-1,1,1,2,3-pentafluoropropane, 1-Chloro-1,1,2,2,3-pentafluoropropane, 2-Chloro-1,1,1,3,3-pentafluoropropane, 1-Chloro-1,1,3,3,3-pentafluoropropane, 1,1,1,2,2,3-Hexafluoropropane, 1,1,1,2,3,3-Hexafluoropropane, 1,1,1,3,3,3-Hexafluoropropane, 1,2,2,2-Tetrafluoroethyl difluoromethyl ether, Hexafluoropropane, Tetrachlorofluoropropane, Trichlorodifluoropropane, ichlorotrifluoropropane, 1,3-Dichloro-1,2,2-trifluoropropane, 1,1-Dichloro-2,2,3-trifluoropropane, 1,1-Dichloro-1,2,2-trifluoropropane, 2,3-Dichloro-1,1,1-trifluoropropane, 1,3-Dichloro-1,2,3-trifluoropropane, 1,3-Dichloro-1,1,2-trifluoropropane, Chlorotetrafluoropropane, 2-Chloro-1,2,3,3-tetrafluoropropane, 2-Chloro-1,1,1,2-tetrafluoropropane, 3-Chloro-1,1,2,2-tetrafluoropropane, 1-Chloro-1,2,2,3-tetrafluoropropane, 1-Chloro-1,1,2,2-tetrafluoropropane, 2-Chloro-1,1,3,3-tetrafluoropropane, 2-Chloro-1,1,1,3-tetrafluoropropane, 3-Chloro-1,1,2,3-tetrafluoropropane, 3-Chloro-1,1,1,2-tetrafluoropropane, 1-Chloro-1,1,2,3-tetrafluoropropane, 3-Chloro-1,1,1,3-tetrafluoropropane, 1-Chloro-1,1,3,3-tetrafluoropropane, 1,1,2,2,3-Pentafluoropropane, Pentafluoropropane, 1,1,2,3,3-Pentafluoropropane, 1,1,1,2,3-Pentafluoropropane, 1,1,1,3,3-Pentafluoropropane, Methyl pentafluoroethyl ether, Difluoromethyl 2,2,2-trifluoroethyl ether, Difluoromethyl 1,1,2-trifluoroethyl ether, Trichlorofluoropropane, Dichlorodifluoropropane, 1,3-Dichloro-2,2-difluoropropane, 1,1-Dichloro-2,2-difluoropropane, 1,2-Dichloro-1,1-difluoropropane, 1,1-Dichloro-1,2-difluoropropane, Chlorotrifluoropropane, 2-Chloro-1,2,3-trifluoropropane, 2-Chloro-1,1,2-trifluoropropane, 1-Chloro-2,2,3-trifluoropropane, 1-Chloro-1,2,2-trifluoropropane, 3-Chloro-1,1,2-trifluoropropane, 1-Chloro-1,2,3-trifluoropropane, 1-Chloro-1,1,2-trifluoropropane, 3-Chloro-1,3,3-trifluoropropane, 3-Chloro-1,1,1-trifluoropropane, 1-Chloro-1,1,3-trifluoropropane, 1,1,2,2-Tetrafluoropropane, ethyl 1,1,2,2-tetrafluoroethyl ether, Dichlorofluoropropane, 1,2-Dichloro-2-fluoropropane, Chlorodifluoropropane, 1-Chloro-2,2-difluoropropane, 3-Chloro-1,1-difluoropropane, 1-Chloro-1,3-difluoropropane, Trifluoropropane, Chlorofluoropropane, 2-Chloro-2-fluoropropane, 2-Chloro-1-fluoropropane, 1-Chloro-1-fluoropropane, Difluoropropane, Fluoropropane, Propane, Dichlorohexafluorocyclobutane , Chloroheptafluorocyclobutane, Octafluorocyclobutane, (Perfluorocyclobutane), Decafluorobutane (Perfluorobutane), 1,1,1,2,2,3,3,4,4-Nonafluorobutane, 1,1,1,2,3,4,4,4-Octafluorobutane, 1,1,1,2,2,3,3-Heptafluorobutane, Perfluoropropyl methyl ether, Perfluoroisopropyl methyl ether, 1,1,1,3,3-Pentafluorobutane, Dodecafluoropentane (Perfluoropentane) , and Tetradecafluorohexane (Perfluorohexane).
[0132] The performance of latent heat exchange can be increased if (a) a liquid droplet or gas bubble or solid phase formed on the surface is highly mobile and can be removed quickly from the surface to minimize the thermal passivation of the active surface under consideration and (b) the thickness of these thermal barriers (droplets, bubbles, solid phase) can be kept small either by promoting quick removal or by promoting dropwise deposition instead of filmwise deposition on the active surface under consideration. When a droplet or a bubble or solid phase is nucleated and the size of it grows (e.g., by nucleation and growth), there is a minimum size (aka. critical droplet size, D crit , or departure diameter) for the droplets or bubbles to spontaneously leave the surface owing to the gravitational force (for droplets and solid phase) or buoyancy force (for bubbles) overcoming the forces associated with the interfaces (i.e. surface tension, wettability, adhesion). Upon the departure of a droplet or bubble or solid phase from the surface, a fresh active surface is regenerated promoting new droplet/bubble/solid phase nucleation and growth, so that enhanced latent heat transfer can be achieved. For example, in the case of shedding droplets on an inclined surface, a shedding droplet can pick up other small droplets via coalescence along its pathway to further enhance the regeneration of fresh surfaces. Localized fast growth of droplets/bubbles/solid phase is preferred and often observed via coalescence, which is also known to occur preferentially along the topographically raised regions (e.g. convex regions) of a given surface due to focusing effect of diffusion flux of incoming phase before phase change. For simplicity, the behavior of phase-change materials is discussed referencing water condensation, but it is understood that the principles and components described herein apply to gas phase and solid phase condensation and heat exchange.
Heat Exchanger/Condenser Design
[0133] In one aspect of the invention, a SLIPS-based surface that is useful as a heat exchanger or condenser includes submicrometer to centimeter scale features on SLIPS-treated surfaces. Exemplary devices are illustrated in FIGS. 1A (i)-(iii), according to one or more embodiments. FIG. 1( i ) shows a surface 100 having a raised convex feature 110 (shown here as a hemisphere). Droplet, bubble, or solid particle nucleation and growth starts at the features apex 120 . Droplet growth is more efficient and droplets 145 formed the raised feature, and in particular near apex 120 , are larger than droplets 140 formed on adjacent flat surface. When the particle reached a critical size, its sheds. In symmetrical systems such as in FIG. 1( i ) , shedding is non-directional. FIG. 1 ( ii ) shows a surface 100 ′ having a raised convex feature 110 ′ and an asymmetric slope 130 ′ extending from apex 120 ′ and transitioning tangentially into the flat surface. Droplet bubble or solid particle nucleation and growth starts at the features apex 120 ′. Droplet growth is more efficient and droplets 145 ′ formed the raised feature, and in particular near apex 120 ′, are larger than droplets 140 ′ formed on adjacent flat surface. When the particle reached a critical size, its sheds directionally down slope 130 ′. FIG. 1 ( iii ) shows a surface 100 ″ having a raised convex feature 110 ″ and an asymmetric slope 130 ″ extending from apex 120 ″ in more than one direction and transitioning tangentially into the flat surface. Droplet bubble or solid particle nucleation and growth starts at the features apex 120 ″. Droplet growth is more efficient and droplets 145 ″ formed the raised feature, and in particular near apex 120 ″ are larger than droplets 140 ″ formed on adjacent flat surface. When the particle reached a critical size, its sheds directionally down any one of slopes 130 ′. FIG. 1B (iii) shows a film 105 that is bearing the bumps and attached to the substrate.
[0134] In some embodiments, the device can be coated with a slippery surface that improves the shedding and droplet collection. Exemplary devices are illustrated in FIGS. 1B (i)-(iii), in which similar elements are similarly labeled, according to one or more embodiments. In each of these devices, a slippery layer 160 covers the device. The slippery layer can be a SLIPS coating. SLIPS coating provides functionalized nano/microasperities or nano/micropores that entrain a lubricating liquid, which fills void spaces, due to capillarity, and lock the lubricating liquid in and on the surfaces due to proper functionalization of the solid that provides chemical affinity to the lubricant, resulting in a molecularly smooth, slippery upper liquid surface. The underlying substrate need not be flat (e.g., an infinite radius of curvature), but can also be curved (but not that the radius of curvature for the raised features is smaller than that of the underlying substrate), as is shown in FIG. 1B (iii).
[0135] When used as a heat exchanger, the features and substrate can be made of thermally conductive components typically used in heat exchangers (e.g., aluminum, copper, stainless steel, etc.). In one or more embodiments, the latent heat exchanger includes a metal (or other thermally conductive polymeric or ceramic) substrate having a plurality of raised or recessed features. In one or more embodiments, the polymer or ceramic can include embedded metal to improve thermal conductivity. In one or more embodiments, embedded metal can be a metal mesh or metal particles.
[0136] When used as a condenser, the substrate and macro-scaled features are not required to be thermally conductive and can be made of polymers. The use of polymers, imparts the ability to create devices that are flexible and dynamically bendable or stretchable (deformable).
[0137] The raised or recessed features include a convex surface or an edge or rim feature on the surface that assists in nucleation and growth. The substrate containing the raised or recessed features contains a further hierarchy of surface treatment and includes a nano/micro-scale roughened surface and a lubricating liquid wetted and adhered to the roughened surface to provide a liquid overlayer within and over the roughened surface to form a repellant surface. The raised features can have a width and height in the range of 100 nm to 10 cm, or more specifically on the order of micrometers to centimeters, or more specifically on the order of hundreds of micrometers to tens of millimeters. In some embodiments, the features can have a height in the range of 100 μm to 5 cm, 0.5-2 mm or in the range of 1-10 mm. In one or more embodiments, the feature height is smaller than the depletion layer, H<δ (the dashed line denoted in FIG. 2C ), so that diffusion is the dominant mechanism of mass transport. In some embodiments, the features can have a width on the dimension of the condensing droplets. In one or more embodiments, asymmetric structures have a scale that is similar to the shedding droplets (diameter ca. 0.6 mm). The features of the roughened surface are on a scale that are significantly smaller than the raised surface features used to condense and shed droplets.
[0138] The entire surface of SLIPS-based heat exchanger, including the raised or recessed features, is treated to form a SLIPS low friction surface ( FIG. 1B (i)-(iii) and FIG. 17A-17E .). The SLIPS comprises functionalized nano/microasperities or nano/micropores (with the roughness factor from 1 representing a largely flat surface, to infinity representing a highly porous solid) that entrain a lubricating liquid, which fills void spaces, due to capillarity, and lock the lubricating liquid in and on the surfaces due to proper functionalization of the solid that provides chemical affinity to the lubricant, resulting in a molecularly smooth, slippery upper liquid surface (see FIG. 1B (i)-(iii)). FIGS. 17A-17E provide exemplary surfaces with immobilized lubricant overlayer: A) nano/microtextured surfaces with the roughness factor R>1; B) largely flat surfaces that utilize the natural roughness of the material (R=1); C) nano/microtextured surfaces with the roughness factor R>1 with the lubricant conformally coating the nano/micro-asperities.; D) nano/microtextured curved surfaces having a positive radius of curvature with the roughness factor R>1 with the lubricant conformally coating the nano/micro-asperities; and E) a nano/micro/milliscale flexible solid film layer 1770 (e.g., PDMS) that can hold and diffuse nano/microdroplets of lubricant. The features can be incorporated into a pipe structure and can be made on a region of the pipe (as shown) or over the entire surface. The elements are similarly labeled in each figure, indicating the substrate 1700 ; a nano/micro texture 1710 ; a functionalized interface 1720 that has high affinity to a lubricant (can be the natural chemistry of the substrate); a lubricant 1730 ; and a stabilized slippery liquid interface 1740 formed on the substrate.
[0139] The nano/micro-scale roughened surface with overlaying immobilized lubricating liquid is referred to as a SLIPS surface. See, International Appin. No. PCT/US12/021928 and International Appin. No. PCT/US13/50364, the contents of which are incorporated by reference, for additional information on preparation and function of SLIPS surfaces.
[0140] FIG. 4D is a profilometer image (oblique view) of a SLIPS-treated raised feature according to one or more embodiments. The raised feature (here an asymmetric bump having tangentially connected slope) on a scale of microns to millimeters (ca. 600 μm) is covered with a surface nanostructure containing nano-scale asperities (ca. 100-200 nm) that are infused with lubricant to create a molecularly smooth slippery coating.
[0141] Without being limited to any specific mode of operation, it is believed that droplets grow faster on the raised surfaces because the depletion layer or boundary layer or the distance from the solid surface to the liquid/vapor interface is thinner. Boundary layer thickness varies due to the raised features and is thinnest at the tips of the raised features. Vapor is transported to the solid surface by diffusion, but in the case of raised surface the boundary layer is thinned, so that droplet formation is sped up. Droplet shedding is enhanced due to the low friction of the SLIPS surface.
[0142] A heat exchanger or condenser according to one or more embodiments is illustrated in FIGS. 2A and 2C . FIG. 2A is an optical profilometer image of an exemplary convex raised structure or “bumps” that can be used for the SLIPS-based heat exchanger surfaces, according to one or more embodiments. In one or embodiments, the substrate has a plurality of raised features. In other embodiments, the substrate can have a plurality of recessed features. FIG. 2C shows a surface having an array of convex structures that can be used for the SLIPS-based heat exchanger, according to one or more embodiments. FIG. 2D shows time-lapsed images of droplets growing by condensation on the apex of the bumps (top row) compared to a flat region with the same height H (bottom row). The largest droplet in each series is denoted by dotted circles at each time point. Thus, raised features having convex surfaces demonstrate more rapid droplet condensation than flat surfaces.
[0143] In one or more embodiments, the structure can be based on a hemisphere as is schematically illustrated in FIG. 11 . FIG. 11 is a cross-sectional schematic illustration of the convex structures showing the dimensions of height (H), radius (R bump ), radius of curvature (κ −1 ) and periodicity (P pattern ) of the features. The raised feature can be based on other curved surfaces, such as ellipsoids and cones. In one or more embodiments, the radius of curvature can be in the range of about 100 nm (˜nucleation size)to 10 cm (˜industrial pipe radii).
[0144] The convex macroscopic surface topography, e.g., having a positive radius of curvature κ —1 , such as the convex structures shown in FIGS. 2A, 2C and 11 , is capable of controlling diffusion flux.
[0145] In one or more embodiments, the structure can be based on other geometries, such as cubes, rectangular prisms, cylinders, pyramids and the like. Exemplary structures are shown in FIG. 3C , and can include rectangular prisms, cubes, truncated cones, truncated pyramids, hemispheres, hemi-ellipsoids, hemicylinders and the like. In some embodiments, the raised features include edges 200 used for mass nucleation and growth, such as the rectangular geometry illustrated in FIG. 13 . Edges, ridges or rims can be viewed as structures having a flat upper region 1300 bordered by rounded edges 1310 having a small radius of curvature around the perimeter. FIG. 13 is an infrared camera image (bottom) of the rectangular bump (top, optical camera image), which shows no distinct temperature difference between the top flat area of the rectangular bump and the surrounding basal region. The black or dark color in the infrared camera image along the edge of the rectangle is due to the scattering and different reflection of the curved region. FIG. 3D is an optical image of raised rectangular bumps with the same height, but having a range of different widths.
[0146] In one or more embodiments, the walls of the raised features can be sloped to create an inclined transition from the apex of the raised feature and continuing smoothly and tangentially to the substrate. By ‘tangential transition’ as used herein, it is meant that the slope curves gradually to a zero slope, without an abrupt change in angle (relative to the plane of the substrate) that would give rise to a negative radius of curvature or concavity. Surfaces with negative radius of curvature can pin droplets, such as is seen in FIG. 4F . The pinned droplets 700 are adjacent to the vertically inclined walls. Exemplary structures are shown in FIG. 4E (i)-(iv), and can include structures in which all or a portion of the side walls form inclined slopes or ramps 610 from the apex 620 to the substrate. The apex may include truncated upper surfaces to provide upper plateaus 630 and rounded edges 640 with high positive radius of curvature. The isotropic features like the two denoted by asterisks in FIG. 4E (i) can promote droplet removal in any direction, irrespective of the orientation in the gravity field and can therefore be placed randomly on any geometrically convoluted substrate. FIGS. 4E (ii)-(iv) show exemplary hemicylindrical convex structures with tangential connection to the surrounding substrate, which can be easily designed, manufactured at low cost, and significantly increase overall latent heat transfer efficiency, in consideration of downward gravitational force or air flow. FIG. 4E (ii) shows a hemicylindrical convex structure that is horizontally positioned on a vertically positioned flat surface. FIG. 4E (iii) shows a horizontally-positioned hemicylindrical convex structure along the side wall of a vertically positioned cylinder (or pipe or curved surface). FIG. 4E (iv) shows a hemicylindrical convex structure along the apex of a horizontally positioned cylinder. This horizontal hemicylindrical convex structure on a horizontally positioned pipe is designed in consideration of (1) fast growth on a smaller convex structure and (2) shedding droplets from the apex of horizontal pipes, shown in FIGS. 14A-G .
[0147] Both convex (e.g., spherical) and edged (e.g., rectangular) raised features that have functionalized nano/microasperities or nano/micropores with entrained and locked lubricating liquid in and on the surfaces (i.e., SLIPS) demonstrate improved droplet formation (faster nucleation and growth) over a traditional ‘flat’ SLIPS surface.
[0148] In one or embodiments, the latent heat exchanger or condenser includes a substrate having a plurality of raised or recessed features in combination with the slope that form an asymmetric feature to provide directional removal of droplets, bubbles or solids. The asymmetry can be achieved by a slope that extends outward from the feature apex in one direction. The asymmetry facilitates directed droplet movement, forced coalescence into larger droplets that can be easily removed in the gravity field, and rapid shedding. In one or more embodiments, the dimension of the asymmetric feature can be in the range of 100 nm to 10 cm, or more specifically on the order of micrometers to centimeters, or more specifically on the order of hundreds of micrometers to tens of millimeters. In some embodiments, the features can have a length or width in the range of 100 μm to 5 cm, 0.5-2 mm or in the range of 1-10 mm. In one or more embodiments, asymmetric structures have a scale that is similar to the shedding droplets (diameter ca. 0.6 mm).
[0149] As is discussed in greater detail herein below, an exemplary asymmetric feature can be a side wall having a width at the basal surface, which is greater than the width of the feature at its pinnacle, and the side wall increases in width or spans outward as it approaches the basal surface. The gradually increasing width of the side wall of the raised feature increases droplet growth and shedding because the asymmetric geometry induces directed motion of the droplets nucleated on the raised features, such that they are forced to coalesce and grow by absorbing other droplets along their moving path, resulting in the fast shedding of the heavy, large droplets in the gravity field. Such devices having asymmetric raised or recessed surface features can be alternatively referred to herein as “SLIPS-A”—slippery surfaces with asymmetric surface features.
[0150] In one or more embodiments, the asymmetric raised feature can include a gradually sloping or inclined ramp or wall that provides a transition from a high point of the raised features to the basal surface of the heat exchanger. The transitional feature or “ramp” is positioned to create an asymmetric structure; the ramp feature is preferably positioned on the surface, so as to direct the shedding droplet in a desired direction. FIG. 4A is a schematic illustration of an asymmetric feature illustrating the basis for directional shedding. The symmetric feature 300 (shown left) possesses four equivalent sides, or walls 310 . Droplet 315 can shed in any of the directions noted by arrows 320 . In contrast, asymmetric structure 330 shown in FIG. 4B includes a high point 340 and a ramp 350 that extends from the high point along one side to create an asymmetry in the profile. The ramp 350 is narrower where it meets the high point 340 than where it meets the basal surface 360 . As the ramp approaches the basal surface 350 , the width of the asymmetric feature increases, the height of the asymmetric feature decreases, and the asymmetric feature merges tangentially with the basal surface. Droplet 370 sheds preferentially in the direction noted by arrow.
[0151] FIG. 4H (i)-(iii) is a series of photographs of a SLIPS-A surface such as shown in FIG. 4B . The raised features have an upper surface 440 having a width of about 0.2 mm; a ramp 450 extends from the pinnacle towards the lower edge of the photographs, gradually increasing in width to about 1 mm. Droplets form at the upper surface of the asymmetric feature and move down along the ramp due to gravity and the ramp incline. The location of the ramp can serve to direct the droplets from the upper surface in a selected direction. The series of photos is a time-lapse series showing droplet condensation and shedding in a moist atmosphere. Faster time for shedding droplets is observed due to the topographically-preferential condensation, forced coalescence, and negligible friction of SLIPS-A. The arrow points at the shedding droplet on SLIPS-A, which grows and begins to move faster than the droplets on flat SLIPS (surrounding area). The state-of-the-art superhydrophobic surface (SHS) shown in FIG. 4G (iv) and a superhydrophobic surface that has a similar asymmetric feature (shown by dashed lines) (SHS-A) shown in FIG. 4G (v) do not show droplet shedding for >20× extended duration of experiment under identical conditions with droplets that reach at least 3 times larger radius before they begin to move, regardless of the presence of the asymmetric feature.
[0152] In one or more embodiments, the latent heat exchanger can include asymmetric features that rely on grooves or troughs recessed into a SLIPS treated surface to improve droplet formation and shedding. The groove or trough recess portions of the SLIPS-treated surface create edges so that the moist air perceives the planar features to be “raised” relative to the recessed grooves and condenses on the planar features faster.
[0153] FIGS. 3A-3B and 5 illustrate this principle of enhanced nucleation and growth due to raised features (edge elements) and asymmetric structure design.
[0154] FIG. 3A shows side and top views of raised features 520 , illustrating flat upper surface 525 , the edge features 530 and condensed droplets 540 , 550 . Droplets 540 growing along edges 530 are larger those growing on the flat surface 525 at the same time point. In one or more embodiments employing convexity effects that induce relatively higher growth rate of condensed droplets in terms of volume, all the dimensions—width (W), spacing (D), height (H), and length (L) can be greater than the critical shedding droplet diameter. In one or more embodiments, the width (W) or spacing (D) of grooves can be smaller than the critical shedding droplet size. In this embodiments, the time to reach the critical shedding droplet diameter can be reduced by forced coalescence that makes two adjacent droplets faster growing along the edges touch each other in a confined geometry defined by the distance between growing edges. FIG. 3B is a side view of two condensed droplets 540 , 540 ′ growing on the edges 550 . The growing droplets along two adjacent edges are about to touch, leading to a forced coalescence of the droplets.
[0155] FIG. 5 is an image of a SLIPS-treated surface having a number of recessed features, e.g., grooves 510 . While making reference to a recessed groove, the principle applies equally to raised asymmetric features. At its widest and deepest point, groove 510 has a width (W) and a depth (−z) and adjacent grooves form a ridge 515 having a dimension defined by the spacing D(z). The groove width tapers to a narrow gap 520 along its length (L) as the groove becomes shallower, eventually becoming level and merging with the SLIPS surface (z=0). In one or more embodiments, the angle of asymmetric grooves can be sharp enough to easily release the droplets condensed in the grooves and the length of the structure (a function of the angle of asymmetric grooves) can be sufficiently long so that the residual droplets near the tail of the grooves can also be removed by the shedding droplets. The width of the ridge 515 is at its narrowest at the mouth 560 of the groove and increases along length L. In operation, droplets 570 formed at the top of ridge 515 coalesce to form larger droplet 570 , which continues to grow (by coalescence with smaller droplets) as it continues along the ridge. Gradually increasing width of ridge increases droplet growth and shedding because the shedding droplets grow by absorbing other droplets along their moving path. See, e.g., droplet 570 .
[0156] FIG. 6 shows the formation and shedding of condensed water droplets on SLIPS (left) and SLIPS-A (right), in which regularly spaced grooves are located at the upper edge of the sample. Droplet shedding performances is summarized in Table 1, where frequency (mHz=10 −3 Hz) refers to the number of droplets formed per second; diameter (mm) refers to droplet size upon shedding and volume flow rate (mL/hr/m 2 ) refers to the volume of shedded droplets collected in an hour in a 1 m 2 area, passing the bottom horizontal dotted line 600 in FIG. 6 .
[0000]
TABLE 1
Results of the image analysis of shedding droplets on SLIPS and SLIPS-A.
SLIPS
SLIPS-A
Avg. Frequency (mHz)
8.9
11.1
Avg. Diameter (mm)
1.92
2.27
Avg. Volume Flow Rate
43.2
77.4
(mL/hr/m 2 )
[0157] The values are averaged for the 180 images recorded for the last 30 minutes of 2 hour long experiments. The averaged volume flow rate is calculated with the measured water contact angle of 105° on the Carnation mineral oil (Sonneborne) used as a lubricant. As shown in Table 1, the SLIPS-A sample exhibits higher average frequency and diameter of shedding droplets compared to ‘flat’ SLIPS. This results in nearly 80% increase in average volume flow rate of condensed water droplets passing the horizontal line 600 shown in FIG. 6 .
[0158] To further examine the effect of increased amount of condensed water (SLIPS-A) on latent heat transfer, overall heat transfer coefficient (OHTC) was measured using a serpentine-shaped setup and conditions shown in FIG. 7 . These measurements show more than 100% enhancement in OHTC compared to typical superhydrophobic surfaces (expected to be a promising candidate for enhanced heat transfer), implying the extremely promising potential of SLIPS-A for a broad range of applications.
[0159] In one or more embodiments, a plurality of raised structures of the same geometry and feature sizes or of slightly different geometry and feature sizes on SLIPS-A can be arranged in a manner that the features form a row or an array where adjacent features in the same row or in the neighboring rows can be aligned (eclipsed) or staggered to cover the surface of heat exchangers. In one or more embodiments, a plurality of raised features on SLIPS-A can be placed on a tubular object, such as pipes or tubes, as well as on a fin-like object, such as cooling fins, in a similar arrangement described above to cover the surface of the tubular or fin-like object and induce accelerated directional shedding of the droplets. In one or more embodiments, the coverage of such a set of raised features can be uniform or randomly distributed over the heat exchanger surfaces. In one or more embodiments, the coverage of such a set of raised features can exist in a pattern on the heat exchanger surface to induce rapid condensation, forced coalescence, and shedding only on a given area. Any combination of the above arrangements is possible.
[0160] In one or more embodiments, a plurality of features is arranged on a surface to increase condensation efficiency across a preselected area. As shown FIGS. 5 and 6 , the features can be arranged in a row. In other embodiments, a number of rows can be employed. The features can be aligned in rows and columns, as illustrated in FIG. 2C and 4K . The features can be located in row that are staggered or offset to increase coverage of condensation run-off. In one or more embodiments, the density of features is selected to optimize condensation efficiency. Referring to FIG. 11 , in which the feature size is described in terms of radius of curvature of the feature R bump and feature to feature spacing P pattern , it has been observed that at less than a critical value (e.g., P pattern /R bump <2.5) the raised features compete for condensation and no additional enhancement in condensation is observed. Thus in determining the features density for a feature with a given R, improvements in condensation can be achieved by approaching a P pattern /R bump of about 2.5 or greater than 2.5.
[0161] These SLIPS with convex asymmetric features (SLIPS-A) offer transformative technology that allows for significant reduction of energy consumption and for increased functional efficiency of various phase change handling applications, e.g., condensation systems.
[0162] The heat exchanger surface according to one or more embodiments possesses a variety of features to achieve fast growth and shedding of droplets. First, higher growth rate in terms of droplet volume is observed on the convex regions of surface features, frequently observed in nature such as on insect wings and referred to as a ‘convexity effect.’ Second, forced coalescence can be achieved by making two adjacent droplets to touch each other. The convexity effect and forced coalescence can make droplets to grow faster to reach the critical shedding droplet size. Lastly, shedding droplets can be guided using gradually increasing width of the raised feature because directional movement of the shedding droplets induces fast droplet growth due to the coalescence with other droplets along their moving path and resulting in increased velocity of the shedded condensate. While each of the surface features of the heat exchange surface described herein contribute to rapid growth and shedding of droplets, combining the described features of the multi-scale surface structures provided greater enhance and improved droplet growth and transport. Therefore, combinations of the features described individually are contemplated with the scope of the invention.
[0163] The aforementioned principles can also be applied for the bubble formation in the process of boiling liquids. In this case, the buoyancy force is “upward”; therefore we can consider the direction opposite to the direction of gravitational force for the bubble motion, once the bubbles reach the critical size that balances the buoyancy force and pinning force. On top of the frictionless mobility, yet another essential benefit of SLIPS and SLIPS-A compared to typical surfaces with extreme wettabilities (e.g., superhydrophobic, superoleophobic, superhydrophilic or superoleophilic surfaces) is that the contact angle of liquid is more or less 90°, which shows extremely low pinning behavior for both droplets and bubbles at the same time. On the other hand, superhydrophobic or superoleophobic surfaces show extremely high pinning force for vapor bubbles because the “contact angle” of bubbles is nearly 0°, forming “film” of vapor that significantly lowers heat transfer performance in boiling.
Device Fabrication
[0164] The substrate can made of a variety of materials capable of introducing the raised or recessed features disclosed herein.
[0165] In some embodiments, the underlying substrate is a thermally conductive base, and can be made, for example, of metal (copper, aluminum, stainless steel, titanium alloy, etc.), conductive polymer, conductive ceramic or other thermally conductive surfaces for heat exchangers. The base is molded into various shapes including tubes, fins, shells, etc. In other embodiments, the substrate is not required to be thermally conductive. For example, condensation can be achieved by condensation without thermal conduction as a primary mechanism. For example, the heat may be transferred by radiation. The underlying case can be a non-conductive polymer or cement.
[0166] A raised or recessed feature can be formed by conventional mechanical/material manufacturing process ranging from pressing, to casting, imprinting, molding, hydroforming, rolling, extrusion, expansion, notching, stamping, embossing, welding, bonding, engraving, machining (e.g. cutting, laser cutting, water jet cutting), etching, 3D printing, and so forth.
[0167] Once a metal-containing surface is formed, the metal-containing surface can be chemically modified to form a surface structure with proper feature sizes, volume, density, and morphology, suitable as a porous surface for SLIPS. The nano/micro-structured surface used to create SLIPS can be made by any method. Suitable methods have been previously described and include optional chemical functionalization to render the roughened surface compatible with the lubricating liquid. See, e.g., International Appin. No. PCT/US12/021928 and International Appin. No.PCT/US13/50402, contents of which are incorporated herein in their entirety.
[0168] Any roughening processes known in the art may be used. Exemplary processes for roughening include application of liquid phase material (paint or ink, spray, spin, dip, air brush, screen printing, inkjet printing), deposition or reaction of gas phase material (CVD, plasma, corona. ALD, PVD), etching, spraying, sputtering or evaporation of metal or metal oxide, composite phase material deposition (particle+binder), electrodeposition or other solution phase growth of material (conducting polymer, electroplated metal, electrophoretic deposition of particles, surface-initiated polymerization, mineralization), gas phase growth of material (nanofibers), multiple layer deposition (repeated coating by layer-by-layer deposition), self-assembly of precursor material (minerals, small molecules, biomolecules, polymers, nanoparticles, colloids), or growth of layers by oxidation-transfer coating and printing (contact printing, pattern transfer). Base materials without additional roughening that exploit the natural roughness of the material (R=1) followed by chemical functionalization and application of the lubricant layer can be used as well (see FIG. 1B )
[0169] In one or more embodiments, metal surfaces can be transformed into porous surfaces having a high roughness factor by chemical treatment such as wet chemical reaction, hydrolysis, alcoholysis, solvolysis, acid-base reactions, hydrothermal or solvothermal reactions, electrochemical deposition or etching, oxidation, plasma etching, chemical vapor deposition or atomic layer deposition, sol-gel reaction, and the like. An exemplary surface roughening process includes the transformation of the surface layer of aluminum into a highly nanoporous boehmite. In some embodiments, a roughened surface based on a metal-containing compound can be fabricated directly on a pure metal substrate (e.g., a bare aluminum plate). In some embodiments, a roughened surface based on a metal-containing compound can be fabricated on a thin metal film created on a metal or nonmetal substrate. The thin metal film can be deposited on the substrate using conventional methods such as vapor deposition (chemical vapor deposition (CVD). atomic layer deposition (ALD), physical vapor deposition (PVD), etc.), sputter deposition, electron beam evaporation, electro or electroless plating, and the like. In some embodiments, a roughened surface based on a metal-containing compound can be fabricated on a metal containing solution-based mixture (e.g., sol-gel coating) deposited on a metal or nonmetal substrate. The solution-based mixture can be applied by various application methods including dipping, spraying, painting, etc. Once formed, the metal layer is reacted, e.g., with water, air, alcohol or acid, to form a nanostructured oxide or oxyhydroxide. Further details for the formation of a nanostructures metal-containing surface can be found in International Appin. No. PCT/US13/50364, contents of which are incorporated in their entirety by reference.
[0170] Once the desired surface micro- or nano-structure is formed, it can be further chemically functionalized to provide the desired chemical affinity for the lubricating liquid. For example, the resulting structured surfaces can be further functionalized for appropriate compatibility with the lubricating liquid (e.g., using silane, thiol, carboxylate, phosphonate, phosphate, etc. as a reactant).
[0171] The lubricant layer is desirably immiscible with the operating materials used for phase change. In one or more embodiments, the lubricating liquid can be a hydrophobic liquid, as mineral oil, silicone oil or hydrocarbon oils. In other embodiments, the lubricating liquid can be an omniphobic liquid, such a fluorinated and perfluorinated oils.
[0172] The lubricating layer may serve as an additional thermal resistance layer on the latent heat exchanger. The effect of an additional lubricant layer should be considered in terms of thermal conductivity, thickness, surface tension, viscosity, boiling/melting point, toxicity etc. In one or more embodiments, the lubricant is selected to have a surface tension ranging from 1 mN/m to 1 N/m. In one or more embodiments, the kind of lubricant is selected to have viscosity ranging from 10 −6 Pa·s to 10 6 Pa·s. In one or more embodiments, the lubricant is selected to have boiling point higher than the operation temperature of phase change-based devices. In one or more embodiments, the lubricant is selected to have melting point lower than the operation temperature of phase change-based devices. In one or more embodiments, the kind and thickness of a lubricant is selected to enhance or at least not impair thermal conductivity. In one or more embodiments, the lubricant is selected to have high thermal conductivity, so that the thermal conductivity of the underlying thermally conductive substrate remains accessible. In one or more embodiments, the lubricant can be chosen so that it does not form a wrapping layer on the condensed liquid droplets that remove the lubricant when shed from the surface. Examples include various white mineral oils, poly(alphaolefin), polyalkylene glycol, and modified silicone oil, whose surface tension ensures infusion into nano/microtextured surfaces and the formation of the surface overlayer, but prevents the formation of the complete wrapping layer of condensed droplets. These lubricants can have a range of suitable viscosities, immiscible with the phase-change fluid, high viscosity index, low volatility, low toxicity, low flammability, and low cost. White mineral oil (e.g. Carnation from Sonneborn), which has approximately two times greater thermal conductivity value than fluorinated Krytox lubricants, can be used. The lubricant layer can be spincoated (e.g. at the angular velocity of 2000 rpm), on the nano/micro-structured surface (e.g. on boehmitized, nanostructured aluminum surfaces) to minimize the overall thermal resistance. A rough calculation shows that its overall thermal resistance is equivalent to only 25% of the overall thermal resistance introduced by the water layer on SHS.
[0173] Together with the selection of lubricant and hierarchical structure design, one can facilitate the formation of droplets or bubbles or solid phase with nearly frictionless mobility.
Applications
[0174] Energy-efficient heat transfer through phase change is critical in numerous applications involving thermal to thermal energy conversion such as thermal power plant condensers, harvesters, desalination plants, distillation towers (e.g., hydrocarbons, polyolefins, hydrofluorocarbons), and building thermal/humidity control systems, vapor deposition systems. The latent heat transfer properties of the current invention can provide energy-saving solutions for water harvesters for drinking and irrigational water, multi-stage flash (MSF) desalination plants, vehicle/building air conditioners (i.e., HVAC systems), dehumidifiers, and oil refinery plants (e.g., hydrocarbons, polyolefins, hydrofluorocarbons) that are currently associated with significant energy penalties.
[0175] Thermal power plants are among the most dominant electricity generation facilities in the US. Furthermore, building temperature/humidity control systems and distillation towers use ˜15% and 6% of total energy in the US, respectively. On current thermal power plant condenser surfaces, the growth of droplets to reach the diameter of spontaneous removal (D crit ) is rather slow due to low rate of vapor diffusion and subsequent coalescence, and the spontaneous shedding of strongly pinned condensates can only happen when the droplet size grows larger, e.g., larger than 5 mm. As a result, thick, continuous, and thermally insulating condensate films or large droplets persist on the low-temperature walls which makes the overall heat transfer inefficient and results in the increase of tremendous energy input, increased greenhouse gas emission and increased use of cooling water.
[0000] a. Increased Efficiency in Thermal Power Plant Condensers
[0176] For thermal power plant condensers, high condensation efficiency results in operating the condensers at lower pressures and hence increasing the “pressure drop” of the saturated steam across a turbine, which translates into a potential improvement in energy generation of 20 million MWh/year, equivalent to a net savings on the order of $2 billion yearly (assuming a price of $0.1/kWh).
[0177] In a thermal power plant, fossil fuel is converted to electricity by burning the fuel to boil water to generate steam that drives a turbine attached to a generator. The steam that has passed the turbine is cooled and condensed back to water in a condenser unit, which is then pumped back to a boiler where the fuel is burning. The entire process happens in a closed loop. By lowering the temperature of the steam that has passed a turbine, the latent heat exchanger of the current invention can increase the pressure difference to drive the turbine with higher efficiency. This can be achieved by cooling the steam into tiny water droplets on a surface that is continuously maintained at a cold temperature by pumping cold water inside (i.e. the condenser unit), then removing those tiny droplets as quickly as possible to expose fresh and cold surface for the incoming hot steam. SLIPS-A enables efficient phase transformation (i.e. condensation of water vapor to liquid) to cool down the steam temperature while keeping the condensed water warmer which must be heated again at the boiler by burning fossil fuel to generate high pressure steam.
[0178] To estimate the enhancement of thermal power plant efficiency, which is the source for calculating the potential money and energy saving, we should first understand Rankine cycle, the theoretical model for designing thermal power plants.
[0179] The steam cycle of thermal power plants is composed of the four parts. High temperature steam with high pressure generated from the boiler (Q H , 2→3) rotates the turbine (W T , 3→4). While rotating the turbine, the saturated steam expands, resulting in lower temperature and pressure. It undergoes a phase change from vapor to liquid in the condenser (Q L , 4→1) by heat exchange with coolants. The condensed water is pumped (W P , 1→2) to the boiler and then reused to make this thermodynamic cycle.
[0180] The theoretical efficiency of this thermodynamic cycle, called Rankine cycle, can be calculated by the ratio between the area hatched with solid line (W net=Q H −Q L ) and the area hatched with dotted lines (QH), shown in FIG. 16A . Therefore, to increase this efficiency, we can lower the temperature (T 4 →T 4 ′) of saturated steam transported from the turbine to the condenser based on the comparison of cycle 1234 with cycle 1′2′34′ in FIG. 16B . Physically, this lower temperature leads to lower pressure (P 4′ <P 4 ) of the saturated steam and thus greater pressure difference across the turbine, resulting in more driving force to rotate the turbine blades and theoretical efficiency improvement. Currently, the performance of condensation is plagued by filmwise condensation, which makes the temperature (T 4 ) of saturated steam relatively high. By introducing high condensation efficiency material or coating (SLIPS-A), one can effectively lower this temperature further.
[0000] b. Correlation Between the Low Pressure of Saturated Steam Leaving the Turbine (or Entering the Condenser) and Condensation Performance of the Surface of Condenser
[0181] The very low pressure (P 4 and P 4 ′) of the saturated steam stems from the huge change in the volume of water after phase change from vapor (or steam) to liquid (or condensate) in the process 4→1 or 4′→1′. Therefore, the higher the condensation efficiency at a given temperature, the lower the pressure of the saturated steam.
[0182] This relation is further analyzed and applied after considering the reported values of overall heat transfer coefficient (OHTC) in the literature. Assuming all the heat transferred from the coolant to the surface where condensation occurs is utilized for phase change, overall heat transfer coefficient is proportional to the condensation efficiency. Even traditional ‘flat’ SLIPS shows improved performance compared to other state-of-the-art coatings. SLIPS also presents the potential to lower the vapor pressure, which is the pressure of the saturated steam, for the same temperature and volume flow rate of the coolant. In traditional untreated materials and SHS, OHTC generally decreases as vapor pressure decreases; however OHTC of SLIPS at ˜2.1 kPa is higher than those of other two coatings at ˜2.8 kPa, which means that SLIPS can condense similar amount of steam at lower pressures. See, Xiao et al., SCIENTIFIC REPORTS |3:1988 ↑DOI: 10.1038/srep01988.
[0183] Traditional ‘flat’ SLIPS already provide ˜100% enhancement in OHTC compared to superhydrophobic surfaces (SHS). The application of asymmetric hierarchical structures according to one or more embodiments disclosed herein provides further significant improvement in the OHTC.
[0000] c. Reduced Amount of Cooling Water for Condensation
[0184] The enhanced condensation performance can reduce the amount of cooling water used in thermal power plants, which is typically nearby sea or lake water. In addition to the cost for cleaning the cooling water, it can reduce the electricity used for operating the cooling water pump and give more options for selecting location of the power plants. [U.S. Energy Information Administration, Many newer power plants have cooling systems that reuse water, 2014, http://www.eia.gov/todayinenergy/detail.cfm?id=14971#]
[0000] d. Reduced Energy Usage to Boil the Returning Condensate
[0185] Alternatively, the enhanced condensation efficiency of SLIPS-A can be used to keep the temperature of condensate higher, regardless of the type of operating coolants (e.g., water for water cooled condensers (WCC), air for air cooled condensers (ACC), hydrocarbons, propane, butane, ethylene, ethane, nitrous oxide, sulfur hexafluoride, dimethyl ether, halons, ammonia, sulfur dioxide, fluorocarbons, perfluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, bromochlorofluorocarbons, silicones, hydrofluorocarbons, hydrofluoroolefins, brines, eurammon, azeotropic compound, and compounds of aforementioned refrigerants). This enables reusing the remaining heat in the condensate for boiling and thus saving fuel costs and the use of coolants.
[0000] e. A Solution for Marine and Microbial Fouling Problem
[0186] Many thermal power plants use seawater as cooling water in the condenser and marine fouling causes significant problems ranging from loss in efficiency of cooling water pump and condensers, to mechanical damage, further to the safety of the nuclear power plants, let alone the high maintenance cost. The surfaces can also improve corrosion resistance.
[0187] It has been shown that SLIPS prevent the formation of bacteria, algae, calcareous fouling, and inorganic build-up on its surfaces. The above-mentioned properties of slippery surfaces can be used in various applications, including multi-stage flash (MSF) desalination plants, thermal and humidity management systems for buildings, etc., liquid harvesting by facilitating the condensation of vapor, effective prevention of mechanical failure of underwater ship parts (e.g., motor screws) by the relief of impact of bubbles generated from cavitation, release of bubbles that hinder the transport of liquid in the pipe and release of biofouling and microbial fouling in pipes and HVAC systems.
[0188] The invention is illustrated by reference to the following examples, which are presented for the purpose of illustration and are not intended to be limiting of the invention.
EXAMPLE 1
[0189] Superhydrophobic surfaces and SLIPS with asymmetric structures on the top parts of the vertically positioned surfaces were prepared using the following method, as illustrated in FIG. 8 . First, a thin aluminum piece (60 mm×55 mm×0.16 mm, aluminum alloy 1100, Heatcraft) was flattened and patterned using the two molds which were prepared by 3D printing technique, a high throughput manufacturing method. After asymmetric millimeter-size structures were patterned, the pieces were immersed in the aqueous Alcojet® (Alconox, Inc.) cleaning solution (0.5 w %) for 50 min with sonication. The surfaces were rinsed in deionized water, followed by acetone rinse. Then the cleaned surfaces were immersed in the boiling water for 10 min to boehmitize the surface to create nanostructures. To make the superhydrophobic surfaces (showing the contact angle, CA=155±5°), the samples were subsequently immersed in a solution of an appropriate surface modifier (a perfluoroalkylphosphate ester, FS-100 or a potassium salt of cetylphosphate ester, CPE-K). To form a SLIPS coating, the latter superhydrophobic surfaces were infused with a white mineral oil (Carnation, Sonneborn) using spincoating step (at 2000 rpm for 1 min, resulting in lubricant thickness of ˜5 μm).
[0190] All the condensation experiments were conducted in the transparent humidity control chamber to maintain the desired relative humidity. All condensation experiments were done in a custom humidity chamber composed of a metallic frame with acrylic viewing windows and a door that enabled regulation of relative humidity (RH=60±5%) by a microprocessor controller (Model 5100-240, Electro-tech Systems, Inc.) and ultrasonic humidifier (AOS 7146, Air-O-Swiss) and surrounding ambient temperature (T=23±2° C.). The aluminum samples were mounted by using thermally conductive double-sided tapes (Thorlabs, TCDT1) on the serpentine shaped copper tubes (OD=¼ in), that are flattened to have a flattened width of =8.5±0.5 mm. Vertically positioned flat and bumpy test surfaces (T surface =7.3±0.6° C.) were chilled through the thermal contact (3M™ Scotch Double Sided Conductive Copper Tape, 12.7 mm wide and 0.04 mm thick) with U-shaped copper tube (T tube =2.3±0.3° C.). The temperature of surfaces and copper tube were measured with a digital thermometer.
[0191] The temperature and flow rate of coolant were controlled by a chiller (VWR 1167P or PolyScience 9106). The schematic illustration of the serpentine shaped copper tube structure and experimental conditions are shown in FIG. 7 . The temperatures at the inlet and outlet of the copper tubing system were measured to quantify the overall heat transfer coefficients on the SLIPS and SLIPS-A compared to the SHS. The improvement of >100% for the OHTCs of SLIPS and SLIPS-A was confirmed in the experimental setup that satisfies relevant environmental conditions (humidity>85%, temperature <8° C.). To further examine the effect of increased amount of condensed water achieved by SLIPS-A, overall heat transfer coefficient normalized by the corresponding value for the SHS (OHTC/OHTC sHs ) was calculated based on the temperature measurement at the inlet and outlet of the serpentine-shaped copper tube setup. OHTC/OHTC SHS is defined as,
[0000]
OHTC
OHTC
SHS
≈
T
out
-
T
in
-
Δ
T
baseline
(
T
out
-
T
in
)
SHS
-
Δ
T
baseline
(
eq
.
1
)
[0000] where T out and T in are measured temperature at the outlet and inlet, respectively, and ΔT baseline is the T out -T in of the copper tube system without any mounted samples. Because the fluid properties such as specific heat, viscosity and density as well as temperature and flow rate of the coolant were identical for all experiments, the normalized OHTC value can be calculated according to eq. 1. As shown in the OHTC values normalized by SHS case ( FIG. 10 ), these preliminary measurements show that SLIPS and SLIPS-A have more than 100% enhancement in OHTC compared to the superhydrophobic control. Due to the “flooded condensation”, SHS shows the lowest value, even compared to bare aluminum samples. Traditional ‘flat’ SLIPS exhibits ˜100% improved value because of the enhanced shedding properties facilitated by the friction-free liquid interface. SLIPS-A recorded the highest value (˜150% improvement), which shows an additional significant effect of the asymmetric structures on the droplet growth and shedding frequency. The error bars are from the intrinsic measurement error of resistance temperature detectors (RTDs, Omega, RTD-NPT-72-E-1/4, Class A) used to measure the temperatures at the inlet and outlet of the copper tube system.
[0192] The aluminum samples were imaged using the time-elapsed function of Canon EOS Rebel T4i (period of imaging=5 or 10 s). From the beginning of the experiments, the images were recorded for more than 2 h. Due to the nearly no shedding motion of droplets on the SHS, only shedding behaviors of condensed droplets on SLIPS and SLIPS-A were analyzed by using MATLAB codes developed based on Hungarian algorithm. Because the condensed droplets on the SHS are rarely moved, the condensation behavior of the SHS with asymmetric structures (SHS-A) was similar to that of SHS.
[0193] FIG. 6 shows the formation and shedding of condensed water droplets on SLIPS and SLIPS-A. The measured diameter is converted to the volume of droplets based on the measured contact angle of water droplets (CA=105°) and is reported in FIG. 9 . Each shedding droplet passing the horizontal line 600 in FIG. 6 is represented by a vertical line on the time axis, with the height indicating the volume of the droplet. The bar graph represents the accumulated volume of shedding droplets passing the horizontal line 600 . As seen in FIG. 9 , even a rough, proof-of-concept design of SLIPS-A based on the consideration of the dimension range of interest exhibits higher frequency and volume of shedding droplets compared to SLIPS. This results in nearly 80% increase in total volume of collected condensed water droplets for the same period of time.
EXAMPLE 2
[0194] To access the effect of raised surface features on droplet growth dynamics, hemispherical bumps precisely designed with three important geometrical parameters; radius of curvature, spacing ration, and height were evaluated, as shown in FIG. 11 . The parameters of the geometrical design included hemispherical radius of curvature R bump , spacing between the hemispheres P pattern and hemispherical patterning that can be captured by two dimensionless parameters r drop /R bump and R bump /P pattern , where the r drop refers to the radius of curvature for the condensed droplet.
[0195] The hemispherical bumps were fabricated by pressing aluminum foil (thickness ˜0.15 mm) between three-dimensionally printed polymer molds. To make the surface hydrophobic, liquid-phase surface treatment for 1 hour at 70° C. was followed after 20 minutes of cleaning using Alcojet® and acetone rinse. Water condensation experiments were done in the humidity chamber that enables the regulation of relative humidity at 60% and surrounding air temperature at 22° C. The test surfaces were positioned vertically and artificial humid airflow is introduced onto the surface.
[0196] Vertically positioned flat and bumped superhydrophobic surfaces were chilled through the contact with U-shaped copper tube at the temperature of 4° C. and the resulting condensation of water was captured by the sequential images as shown in FIG. 12 . The center parts of FIG. 12 display water condensation on bumped hydrophobic surfaces whereas outer surroundings exhibit conventional dropwise condensation on the flat hydrophobic surface. Because of no shedding droplets by gravitation forces were observed (the critical shedding diameter>maximum droplet size observed in the experiment), the droplets grow on both surfaces by direct vapor to liquid phase change and coalescence. Due to the nearly uniform surface textures on flat surfaces, droplets grow following a power law on the temporal evolution of the average droplet diameter. In contrast, droplets on bumps grow much faster in the early stage and finally reach the similar diameter to the droplets on the flat surface.
[0197] The quantitative analysis on both flat and representative bumped surfaces for the time range from 500 seconds to 5000 seconds is provided in FIG. 12 . Droplets on bumps grow much faster in the early stage resulting in a higher value for abscissa intercept and finally reach the similar diameter to the droplets on the flat surface, leading to gradually decreasing slope in the log scaled graph, whilst drops on flat regions show lower intercept and constant slope value in the range of observation time. In order to understand this unique droplet growth behavior on flat surface, droplet growth dynamics follows the power law suggested by Beysens et al. (r˜αt β ). Beysens' several studies have also revealed the difference of the coefficient alpha on the perpendicular edge of rectangular structures. However, any systematic study on the condensation characteristics of various geometries (e.g., radius of curvature at the edge, height and width of a convex structure) ranging from simple hemispherical bump to asymmetric features at millimetric length scale has not been reported to the best knowledge of the inventors.
[0198] Qualitatively, droplets grew faster and larger on the peaks of the hemispheres. By measuring the largest droplet diameters at logarithmically spaced time points and fitting a linear regression to the log-log plot of diameter vs. time, the time constant for growth on the bumps was calculated to be 0.60±0.04 or higher depending on experimental conditions.
EXAMPLE 3
[0199] To optimize the focused diffusion flux, predictive models were developed that quantify the magnitude and spatial profile of vapor flux as a function of the radius of curvature. Models for steady state transport of dilute species were used to simulate the magnitude of diffusion flux. The depletion layer thickness (δ˜10 mm>H˜1 mm) was used. Axisymmetric coordinates and two-dimensional coordinates were used for spherical-cap-shaped bumps and rectangular bumps, respectively. The magnitude of the maximum diffusion flux focused at the apex of bumps does not decrease more than 5% if P pattern /R Bump >2.5. See, FIG. 11 . A plot of the simple scaling of diffusion flux near the apex of a spherical cap shows that the smaller the radius of curvature, the greater the localized diffusion flux. See, FIG. 2G .
[0200] Within a narrow region represented by the rectangle in FIG. 2F (i), the concentration gradient near the apex of spherical-cap-shaped bumps can be approximately estimated by converting the bump topography to a sphere with the same radius of curvature, as shown in FIG. 2F (ii) and calculating the concentration distribution created by a mass sink and its mirror image with the same magnitude and the opposite sign (i.e., corresponding mass source that has the same distance from its center to the depletion layer) as shown in FIG. 2F (iii). The concentration distribution at an arbitrary point on the line between the centers of the mass source and sink can be obtained by the superposition of two independent concentration distributions created by the source and sink, respectively. The models indicated that the area where the diffusion flux is greater than on the flat region with the same height becomes increasingly concentrated at and around the apex or the dome, and its maximum intensity grows stronger, as the radius of curvature decreases.
[0201] Consistent with the analytical and numerical models, the largest droplet diameters are experimentally observed at the apex of spherical-cap-shaped surface features that have the smallest radii of curvature ( FIG. 2H ), The radii of curvature for this investigation are set out in Table 2.
[0000] Table 2. Radius of curvature of various bumps used in FIG. 2H from the profilometer images.
[0000] TABLE 2 Radius of curvature of various bumps used in FIG. 2H from the profilometer images. Radius of curvature (mm) Spherical-cap-shaped bump 1 4.2 Spherical-cap-shaped bump 2 1.5 Spherical-cap-shaped bump 3 0.53 Rectangular bump 0.18
However, the rate of droplet growth on the bump with the smallest radius of curvature begins to slow down at later time points (see upper curve in FIG. 2H ). This change of slope suggests that the effect of the focused diffusion flux at the apex diminishes when this region becomes covered by the growing droplet.
EXAMPLE 4
[0202] To maintain the advantages of the small radius of curvature but avoid the decrease in growth rate, a raised feature having a rectangular geometry for the apex was investigated, with a flat region on top bordered by rounded edges as shown in FIG. 3E . This shape incorporates an even smaller radius of curvature around the perimeter, combined with an additional area of focused flux on the top flat area. For a smaller width, the superposition of diffusion flux focused on these features collectively results in a larger contiguous area of high diffusion flux. Droplets on the rectangular structure, therefore, continue growing for a longer time at a constant growth rate, as shown in FIG. 3E , because the coalescence and moving of the growing droplets to the flat top area of the bump continues to provide fresh sites for re-nucleation and growth. FIG. 3E shows time-dependent droplet growth on bumps with decreasing width.
[0203] As the growing droplet does begin to cover the curved edges, the shape of the rectangular structure—flat with curved borders—also lends itself to a mechanism to transport the droplet directionally, when topographical asymmetry is integrated into the design. As previously shown, a droplet growing on a rectangular column will eventually fall off in a random direction. Adding a gradually widening slope descending from one side promotes downward motion by enabling the drop to transition to a completely flat surface. See, FIG. 4B . The total free energy of the droplet-bump-vapor system is lowest when the droplet is on a completely flat region of such an asymmetric convex structure where d=W, as illustrated in FIG. 4C . The upper portion of FIG. 4C shows the same droplet 370 of constant diameter at different positions as it moves along the slope 350 of asymmetric feature 330 , with the corresponding normalized energy in the plot immediately below. At the far left, the droplet is larger than the flat area and overlaps with the low radius of curvature (rounded) edges, providing the normalized energy level for subsequent comparison. The capillary force resulting from this energy profile on a surface with negligible friction would lead the drop to move down the slope toward the wider flat area such that it will no longer overlap with the curved regions (shown as a dark edge band in FIG. 4C ). The droplet shows the minimum energy state when the width of the flat region equals the diameter of the droplet (d=W), and therefore moves down the slope once it grows to cover the curved perimeter.
[0204] Asymmetric bumps with a tangential connection between the descending slope and the surrounding flat regions and having a slippery lubricant-locked nanocoating were fabricated (SLIPS-A). On the fabricated slippery asymmetric structures, droplets move even against gravity, as shown in FIG. 4F , because in such a system the capillary effect is dominant compared to gravitational effect (as captured by the Bond number—the ratio between gravitational force and capillary force−Bo=(ρ water −μ air )gr 2 /γ LV ˜1/7 at the length scale of the droplet, where ρ water and ρ air are the density of water and air, g is the gravitational constant, r is the radius of the droplet, and γ LV is the surface tension of the water-vapor interface). The droplet shown by the arrow in the optical images partially covers the curved border (indicated by a higher reflection that can be seen as a thin bright region between the black sides and the grey flat top) of the asymmetric bump (t−t c =−10 sec, where t c is the time of completed coalescence). This drives it to move up to a wider region (t−t c =−5 sec), where it then coalesces with another drop and moves further up along the bump (t−t c =0 sec). The dotted line tracks the vertical progress of the droplet. Even though the modeling shown in FIG. 4C suggests that the lowest energy point for the moving droplet with a constant diameter is not the bottom of the bump (i.e., its widest region) and the droplet might be expected to be pinned upon reaching the point where d=W, the droplet can keep moving and accelerating as its size grows by coalescing with other small droplets on its path. This is observed by the droplet in FIG. 4F (indicated by an arrow) that merges with a second droplet (for example, as indicated by an asterisk), to form a larger droplet, which results in the condition d>W and drives the coalesced droplet to a location further down the slope, where the condition d=W is again satisfied. This mechanism guides droplet motion solely along the direction determined by the widening slope, regardless of the orientation of the bump relative to gravity. As a further example, FIG. 4G shows time-lapsed optical images of condensed water droplets on an exemplary asymmetric structure in combination with the SLIPS coating rotated 90° relative to gravity showing that the droplet travels solely in the direction determined by the bump geometry until it reaches the end of the bump and makes an immediate 90° turn to align with gravity. The dotted line tracks the horizontal motion of the droplet on the bump.
EXAMPLE 5
[0205] The surface structures according to one or more embodiments that include asymmetric bumps and SLIPS surfaces exhibit droplets that rapidly grow and are shed much earlier as compared to other state-of-the-art surfaces. FIG. 41 provides quantitative analysis of the droplet growth as a function of time, comparing the performance of slippery and superhydrophobic surfaces with and without asymmetric bumps. Both slippery asymmetric bumps (▴) and superhydrophobic asymmetric bumps (Δ) show faster localized droplet growth in the early stage (t<10 3 sec) compared to flat slippery (▪) and superhydrophobic (□) controls. Drops on slippery asymmetric bumps exhibit a further enhanced growth rate (rectangular box in the middle of the plot) as they move down the bump slope, approximately six-fold greater than typical droplet growth dynamics, and the shortest t first (i.e., the average time at which the first three drops are transported solely by gravity) of <˜20 min. Inset shows a magnified view of the fast growth, attributed to positive feedback between coalescence-driven growth and capillary transport. Neither superhydrophobic asymmetric bumps nor flat superhydrophobic surfaces produce shedding droplets within t˜200 min.
[0206] Flat-slippery surfaces outperform superhydrophobic surfaces in droplet size measured at a given time. Moreover, due to the aforementioned diffusion flux at the apex of the convex features, both slippery asymmetric bumps (solid black line) and superhydrophobic asymmetric bumps (dotted black line) show faster localized droplet growth in the early stage (t<10 3 sec) compared to their flat controls. Surfaces with slippery asymmetric bumps show a unique discontinuous behavior, with a slope of ˜0.82 at the early stage and ˜6.4 at the later stage of droplet growth, which is more than six-fold higher than the maximum slope (˜1) observed in typical droplet growth dynamics
[0207] While each of the surface features of the heat exchange surface described herein contribute to rapid growth and shedding of droplets, combining the described features of the multi-scale surface structures provided greater enhance and improved droplet growth and transport. The accelerated growth (slope of 6.4) captured by the magnified view in the inset of FIG. 41 illustrates the feedback between coalescence-driven growth and capillary-driven transport discussed above. As a result, the fast growing droplets on the slippery asymmetric bumps, which are aligned with gravitational force, are delivered to the bottom of the slope at a size where they can then be transported by gravity, while droplets on the adjacent flat slippery surfaces are still far below the critical shedding diameter.
[0208] Droplets shed from the slippery bumps within t first ˜10 3 sec, where t first is the average time at which the first three drops are transported solely by gravity, whereas droplets on other state-of-the-art surfaces grow slowly, and shed much later (e.g. t first ˜4×10 3 sec on flat slippery surfaces) or do not shed for more than t˜10 4 sec (e.g. on superhydrophobic surfaces).
EXAMPLE 6
[0209] An array of asymmetric features in an offset pattern was fabricated (see, FIG. 4K (left)) used the methods described above. The water collection capability was compared to a flat SLIPS surface (se FIG. 4K (right)). The offset placement of asymmetric raised features allowed for the shedding of one set of droplets without interference from nearby raised elements. The volume of collected water for these two surfaces over time is shown in FIG. 4L . Due to the faster droplet growth and transport performance of the SLIPS-A, which yields a continuous, rapid steady state turnover, a slippery surface with an exemplary array of the asymmetric structures showed an order of magnitude greater volume of water turnover compared to the flat slippery surfaces. FIG. 4M shows steady state water collection performance on bumpy (▴) and flat (▪) slippery surfaces. These extended data demonstrate that even with catastrophic shedding (which occurred at t=2 hrs on flat slippery surfaces) taken into account, the continuous turnover rate on the bumpy surface yields substantially more water over time. Shedding on the flat slippery surface does not show multiple shedding cycles because, after the initial catastrophic shedding, drops grow and shed randomly, rather than in periodic or predictable increments whereas the shedding pattern on bumpy surfaces is stable and uniform in time. In our experiments, the time-dependent water collection is intended not only as a measure of water production per se but also as a more general readout of the steady state turnover kinetics. This behavior is the reason synergy between growth and transport is so important. The fast turnover kinetics are established after just a few tens of minutes and then sustained continuously and indefinitely, yielding both a faster response time (time required to collect the first droplet) and an uninterrupted, reliable, and predictable performance over time. The constant faster shedding rate on the slippery surface with asymmetric bumps not only produces more total water but is crucial for many applications beyond simple water collection. This steady-state and predictable behavior is essential for applications such as phase change heat transfer, where a delayed or irregular performance could allow overheating or overcooling. Further, for water harvesting in arid regions, the faster response time is crucial because condensed water droplets will evaporate if they do not shed after a limited time.
EXAMPLE 7
[0210] As a comparison, droplet growth curves were created for four surfaces previously developed for dropwise condensation, such as in heat exchange, dehumidification, and desalination systems. FIG. 4N shows droplet growth curve on four surfaces—macroscopic asymmetric bumps with nanostructure (without lubricant, A, slope=0.62), macroscopic asymmetric bumps with molecularly smooth lubricant (without nanostructure, ▴, slope=0.78), flat slippery coatings (without macroscopic bump, ▪, slope=0.79), and flat hydrophobic surfaces (as a control, ◯, slope=0.86). Whereas slippery flat surfaces (illustrated by curve ▪) showed shedding at t˜4×10 3 sec, the other three surfaces (illustrated by curves Δ, ▴ and ▪) did not display shedding for more than t˜1.2×10 4 sec. The slopes of all the lines are similar to each other because when condensed droplet size is smaller than the radius of curvature of the underlying convex structure, the effect of curvature does not significantly affect the droplet growth exponent.
EXAMPLE 8
[0211] Water vapor condensation on slippery surfaces having raised convex structures without an asymmetric topography were evaluated for droplet growth and shedding. In one example, the raised features were hemispherical and had a radius of curvature in the range of 0.53-4.2 mm. FIGS. 40 and 4P (top) show images of droplets condensed on slippery spherical-cap-shaped bumps and rectangular bumps. FIGS. 4O and 4P (bottom) plot droplet diameter as a function of time for the hemispherical and rectangular prismatic features. The raised features generated condensed droplets of greater size than on the surrounding flat slippery surface. Even with a slippery coating, however, the bumps did not result in droplet shedding within the time studied, although the droplets were greater than the shedding diameter (denoted by the dotted horizontal line) measured on corresponding flat surfaces.
EXAMPLE 9
[0212] The droplet growth rate near the apex and the base of the asymmetric raised features was evaluated. In this example, the fast growth and transport of droplets on slippery asymmetric bump apices were compared to the bottom edge regions. A plot of droplet size over time for slippery asymmetric bumps (▴), edge regions (▪) and flat slippery surfaces (▪) is shown in FIG. 4J . Each data point outside the three circles represents the average size of at least the three largest droplets on each surface. The three circles show the enhanced growth rate for the first three droplets that begin to move down by coalescence-driven growth and capillary-driven motion before leaving the bump and shedding solely by gravity. Each data point inside the three circles represents the diameter of the largest droplet on each of the bumps, obtained by tracking the same droplet on each of three different bumps. This plot demonstrates the superior drop growth behavior on the apex of bumps, compared to the bottom “edge” region.
EXAMPLE 10
[0213] To apply the fast drop growth by the focused diffusion flux on convex surface curvature to another geometry that is widely used in industry, horizontally-positioned pipes with different diameters and the same aluminum thickness, hydrophobic coating, and surface temperature were tested. The quantitative results on the drop growth are shown in FIG. 14C . The pipes evaluated here can be viewed as the macro-scaled features with a positive radius curvature and, although they do not have slippery coatings, the difference in droplet size with pipe diameter (and thus radii of curvature) is an indication of the role surface curvature plays in droplet nucleation and growth. If the pipe surfaces are modified to become SLIPS, most of shedding droplets are observed to start from the top region of horizontally-positioned pipes regardless the diameter of pipes as droplet growth and transport are in steady-state. The shedding droplet volume on the smallest diameter pipe is the smallest because the center of mass of droplets growing on the smallest diameter pipe is more likely to be a position with a smaller elevation or altitude angle where a greater portion of gravitational force acts in the direction tangential to the underlying surface, compared to other greater diameter pipes. FIG. 14E is a plot of initial volume of shedding droplets (N=10), supporting the additional favorable effect of smaller pipe diameter on shedding droplet volume (or size), leading to earlier transport of condensed droplets.
[0214] FIG. 14D is a schematic illustration of a droplet on SLIPS pipe (cross sectional view) of different diameters, showing the effect of diameter of pipes on the magnitude of driving force (gravitational force's component that is tangential to the pipe surface, the length of darker arrows form the center of droplets) of droplet shedding. In the illustration, the size of droplet and the magnitude of gravitational force represented by the arrow pointing toward bottom are the same for the two different diameter pipes but the component of gravitational force tangential to the surface is greater on the smaller diameter pipe compared to the larger diameter pipe. This illustration explains why the size or volume of shedding droplets on a smaller diameter pipe is smaller compared to a larger diameter pipe.
[0215] As a result of enhanced drop growth and transport on a smaller diameter pipe, collected water in the container placed at the bottom of the pipes shows the greatest value in terms of the amount of water per unit area when the diameter of pipe is the smallest, as shown in FIG. 14F . A more collected water per unit area is a good indication of a higher heat transfer coefficient in phase change heat transfer because most of the heat transfer occurs in the process of condensation itself, compared to cooling down the temperature of the condensates.
[0216] Another example of a different radius of curvature geometry was evaluated, as shown in FIG. 14A at 3×10 3 sec. In a cylindrical coordinate, the radius of curvature becomes smaller in the z-direction. FIG. 14B is a plot of droplet size as a function of z at t=1×10 3 (), 2×10 3 (♦), 3×10 3 (▪), and 4×10 3 (A) sec. Only the left end of the conical structure is thermally in contact with the low-temperature copper tube; therefore the temperature on the region with a smaller radius of curvature is higher than the region with a larger radius of curvature. Even against this unfavorable temperature gradient, the smaller radius of curvature regions showed larger droplets compared to the larger radius of curvature regions as shown in FIG. 14B , thus ruling out the role of temperature differences across the surface topography in directing the flux toward the apex of the bumps.
[0217] A further example is shown in FIG. 141 , where a hierarchical structure is provided by forming raised bumps over a hemicylindrical (half-pipe) structure. (shown left). The size of the condensed droplets on the hierarchical structure is greater than that of the condensed droplets on a cylindrical geometry of similar radius of curvature (shown right) under identical condensation conditions.
EXAMPLE 11
[0218] Longevity of SLIPS is essential for reliable enhanced performance of heat exchangers and other relevant applications. FIG. 14G shows an exemplary simple setup for significantly extending the lifetime of SLIPS on pipe geometry. The lubricant can be supplied to horizontal microchannels against gravity by capillary rise in oleophilic material. The horizontal microchannels are located on the top of the horizontal pipe to minimize undesired increase of critical shedding diameter by the microchannels perpendicular to the direction of drop shedding. The horizontal and vertical microchannels are designed based on the faster lubricant transport phenomena by microchannels confirmed in another experiment shown in FIG. 14H . The relatively bright regions along the grid of microchannels represent that the initially dry nanostructured regions are partially wetted by spreading of lubricant that moves along the microchannels faster than nanostructure only region. The cross sectional dimension of and distance between microchannels for replenishing lubricant can be chosen depending on the operating condition and rate of lubricant loss.
[0219] Microchannels that are aligned and perpendicular to the axis of the pipe and the oleophilic material facilitate transport of lubricant from reservoir by capillary effect. In particular, the width and depth of microchannel, as well as the spacing between microchannels can be tuned depending on the condensation condition (e.g., supersaturation, viscosity of lubricant at the pipe surface temperature). In multiple tests, at least an order of magnitude of longer lifetime has been confirmed and constant performance is anticipated as long as the reservoir is full of lubricant.
EXAMPLE 12
[0220] Previous studies on condensation on topographically heterogeneous surfaces have found that the micro/nanoscale concave textures play a major role in preferential condensation if the textured surface is modified with a chemically homogeneous coating. To minimize the effect of the small length scale concave textures (e.g., less than the radius of curvature of the raised feature), the hemispheroidal surfaces were coated with PDMS. Polydimethylsiloxane (PDMS, 10:1 wt % of Sylgard 184 silicone elastomer base:Sylgard curing agent) was spun on the side of interest at 2,000 rpm for 2 min. The thickness of the deposited PDMS is 22.2±3.3 μm, calculated from the measurement of mass difference before and after the deposition. The PDMS-coated surfaces were examined using scanning electron microscopy (SEM) and profilometry. Whereas the uncoated surfaces exhibited microscale roughness, the PDMS-coated surfaces did not display the micro-roughness and were effectively smooth, as shown in FIG. 2B . The droplet growth on these surfaces is shown in FIGS. 2D and 2H .
[0221] To further compare the effect of the micro/nanoscale concave textures and that of millimetric convex topography on droplet growth in condensation, the same macroscopic geometry used in FIG. 2D was tested for droplet growth after roughening the flat surfaces with the 320 grit sandpaper before molding, cleaning and treating them with FS100 a perfluoroalkyl phosphate surface modifying agent. As shown in FIG. 2E , the bump without additional roughening by sandpaper shown still exhibited greater droplets on its apex compared to the roughened flat surfaces, thus ruling out the importance of the surface nano/micro roughness to the observed preferential droplet growth at the apex of the structures.
EXAMPLE 13
[0222] The effect of an applied strain, termed ‘guided coalescence’ on a SLIPS-A surface was evaluated. In some embodiments, the substrate can be stretchable. For example, the substrate can be a stretchable polymer. The polymer can be poorly thermally conductive, thermally conductive or it can include embedded metal to improve thermal conductivity. For example, the metal can be metal particles or metal mesh. The ability to reversibly stretch the device allows for guided coalescence. Guided coalescence permits the controlled disconnection of the nucleation and growth process from the shedding process. By choosing to deform the substrate during a condensation process, it is possible to create asymmetry in the substrate that direct droplet (or bubble or sold) shedding at a time and in a direction that is guided by the deformation process.
[0223] FIG. 15A is a schematic illustration of drop movement and coalescence when underlying stretchable substrate is elongated in y-direction for a flat surface and a bumpy surface. Droplets fast grown on the apex of bumps by focused vapor diffusion flux are moved to concave regions between bumps, created by stretching a bumpy surface, and coalescence of these big droplets is also facilitated due to the suitable design of spacing between adjacent bumps. As a result, droplets not only grow faster on the apex of bumps by condensation but also grow even faster by guided coalescence. The cleaned apex of bumps can become fresh region for re-nucleation and re-growth of condensed droplets and growth/transport can be spatio-temporally controlled and enhanced by this “dynamic harvester” concept. FIG. 15B is a schematic illustration of the fabrication steps for creating a dynamic harvester. To enhance the thermal conductivity of the substrate, a copper mesh was used to create a composite structure material with soft polymers. Pre-stretching is an essential step to maximize the stretching capability of this composite material. FIG. 15C is an image of an exemplary dynamic harvester test setup according to one or more embodiments. FIG. 15D shows results of the condensation experiments using a dynamic harvester. Optical images show the predicted fast drop growth by (unstretched) bumps (a) and the effect of stretching the substrate on further growth by guided coalescence (b). The plot on the bottom right (d) shows gradual drop growth in the process of stretching and relaxing represented by strain-time plot (c).
[0224] Unless otherwise defined, used or characterized herein, terms that are used herein (including technical and scientific terms) are to be interpreted as having a meaning that is consistent with their accepted meaning in the context of the relevant art and are not to be interpreted in an idealized or overly formal sense unless expressly so defined herein. For example, if a particular composition is referenced, the composition may be substantially, though not perfectly pure, as practical and imperfect realities may apply; e.g., the potential presence of at least trace impurities (e.g., at less than 1 or 2%) can be understood as being within the scope of the description; likewise, if a particular shape is referenced, the shape is intended to include imperfect variations from ideal shapes, e.g., due to manufacturing tolerances. Percentages or concentrations expressed herein can represent either weight or volume.
[0225] Although the terms, first, second, third, etc., may be used herein to describe various elements, these elements are not to be limited by these terms. These terms are simply used to distinguish one element from another. Thus, a first element, discussed below, could be termed a second element without departing from the teachings of the exemplary embodiments. Spatially relative terms, such as “above,” “below,” “left,” “right,” “in front,” “behind,” and the like, may be used herein for ease of description to describe the relationship of one element to another element, as illustrated in the figures. It will be understood that the spatially relative terms, as well as the illustrated configurations, are intended to encompass different orientations of the apparatus in use or operation in addition to the orientations described herein and depicted in the figures. For example, if the apparatus in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term, “above,” may encompass both an orientation of above and below. The apparatus may be otherwise oriented (e.g., rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. Further still, in this disclosure, when an element is referred to as being “on,” “connected to,” “coupled to,” “in contact with,” etc., another element, it may be directly on, connected to, coupled to, or in contact with the other element or intervening elements may be present unless otherwise specified.
[0226] The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of exemplary embodiments. As used herein, singular forms, such as “a” and “an,” are intended to include the plural forms as well, unless the context indicates otherwise.
[0227] It will be appreciated that while a particular sequence of steps has been shown and described for purposes of explanation, the sequence may be varied in certain respects, or the steps may be combined, while still obtaining the desired configuration. Additionally, modifications to the disclosed embodiment and the invention as claimed are possible and within the scope of this disclosed invention.
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Sub-micrometer to centimeter scale rough symmetric and asymmetric structures are incorporated onto objects (e.g. tubes and fms). Asymmetric and hierarchically structured slippery structures can be applied to a broad range of materials and shapes of surfaces for manufacturing heat exchangers, dew harvesting devices, desalination devices, de-humidifiers, distillation towers, evaporation coils, anti-cavitation coatings, etc.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part (CIP) of U.S. Ser. No. 13/932,150, filed Jul. 1, 2013, and titled “VIVALDI-MONOPOLE ANTENNA”;
[0002] which claims benefit of priority with U.S. Provisional Ser. No. 61/666,795, filed Jun. 30, 2012;
[0003] the contents of each of which are hereby incorporated by reference.
BACKGROUND
[0004] 1. Field of the Invention
[0005] This invention relates to antennas for wireless communications; and more particularly, to a novel antenna structure herein termed a “Vivaldi-Monopole Antenna” that is configured for ultra-wideband operation.
[0006] 2. Description of the Related Art
[0007] Those having skill in the art will appreciate the difficulty in forming an antenna that exhibits stable radiation performance across the ultra-wide bandwidth, especially where low frequency communications bands are desired.
[0008] For this reason, there is a continued need for ultra-wideband antennas having relatively small form factor for integration with a variety of portable wireless devices.
[0009] In the prior art, an antenna structure known as a “Vivaldi Antenna” is described as having a tapered notch configured to achieve ultra-wide band resonances. Vivaldi antennas are generally understood by those in the art; however, further review of such antennas can be accomplished with an internet search. Accordingly, a detailed review of Vivaldi antennas is not provided herein.
[0010] In the Vivaldi antenna, current distribution tends to travel at the edges of the tapered element. Because of this, low frequency bands are not achievable with the standard Vivaldi tapered slot unless a very large element is provided. However, because large antennas are not desirable with modern electronics, a large conventional Vivaldi antenna is not a suitable solution for applications where ultra-wideband and low frequency characteristics are desired.
[0011] There is a need for ultra-wideband antennas capable of low frequency resonances for use in modern communications devices.
SUMMARY
[0012] A modified Vivaldi antenna, hereinafter referred to as a “Vivaldi-Monopole Antenna” is described.
[0013] The Vivaldi-Monopole antenna is a novel antenna configuration comprising a tapered slot portion and a monopole element for achieving ultra-wideband and low frequency resonance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The Vivaldi-Monopole antenna is herein described with reference to the appended drawings, wherein:
[0015] FIGS. 1(A-B) show a Vivaldi-Monopole antenna in accordance with an embodiment.
[0016] FIG. 2 shows a Vivaldi-Monopole antenna in accordance with another embodiment.
[0017] FIG. 3 shows a sectional view of the Vivaldi-Monopole antenna in accordance with an embodiment.
[0018] FIG. 4A shows a flexible Vivaldi-Monopole antenna fixed at a ninety degree bend within a device housing.
[0019] FIG. 4B shows a flexible Vivaldi-Monopole antenna fixed about a curved surface of a device housing.
[0020] FIG. 4C shows a flexible Vivaldi-Monopole antenna fixed within a round device housing such as, for example, a utility meter.
[0021] FIG. 5 shows a plot of return loss associated with the Vivaldi-Monopole antenna of FIG. 1 .
[0022] FIG. 6 shows a plot of efficiency associated with the Vivaldi-Monopole antenna of FIG. 1 .
[0023] FIG. 7 shows a plot of peak gain associated with the Vivaldi-Monopole antenna of FIG. 1 .
[0024] FIG. 8A shows a current distribution about the Vivaldi-Monopole antenna of FIG. 1 at 700 MHz.
[0025] FIG. 8B shows a current distribution about the Vivaldi-Monopole antenna of FIG. 1 at 3000 MHz.
DETAILED DESCRIPTION OF EMBODIMENTS
[0026] A novel antenna structure, referred to herein as a “Vivaldi-Monopole Antenna”, is suggested for wireless communication across an ultra-wide bandwidth, including the lower cellular bands at 700 MHz, 850 MHz, and 900 MHz, along with higher frequencies in the wireless industry's electromagnetic spectrum.
[0027] The Vivaldi-Monopole antenna comprises a Vivaldi-type tapered slot element and a monopole element. By combining the current distribution modes of the tapered slot element with the monopole element as illustrated herein, an ultra-wideband antenna configured for operation at low band cellular frequencies (ex: 700 MHz-900 MHz) is achieved.
[0028] Now turning to the drawings, FIGS. 1(A-B) show a Vivaldi-Monopole antenna 100 in accordance with an embodiment. The Vivaldi-Monopole antenna 100 comprises a thin rectangular conductor volume 107 extending along a longitudinal axis (L′) from a rear edge to a front edge. The conductor 107 further comprises an aperture 109 having a center thereof disposed near the longitudinal axis, and a first slot 110 extending from the aperture toward a center of the rectangular conductor 107 . At least a portion of the first slot 110 is tapered toward a side edge of the conductor, herein termed the “tapered side” 112 . The first slot 110 forms a tapered slot element 102 that is configured for one or more high frequency resonances. The conductor further comprises a monopole element 101 disposed along the front edge, wherein the monopole element comprises a length of conductor extending from the longitudinal axis toward the tapered side along at least a portion of the front edge. The monopole element 101 is separated from first slot 110 by a lateral slot 111 therebetween, wherein the lateral slot is oriented perpendicular with respect to the longitudinal axis. A signal feed pad 103 and a ground feed pad 104 , respectively, are disposed across the first slot 110 at a point adjacent to the aperture 109 .
[0029] A flexible mini-coaxial cable 105 is shown, wherein the mini coaxial cable comprises a mini-RF connector 106 at a terminal end thereof, and a conductor wire being soldered to each of the ground 104 and signal feed pads 103 , respectively.
[0030] The conductor can be fabricated on a substrate using any electroplating, electro-depositing, printing, or other method known in the art. Moreover, the substrate can be a dielectric substrate.
[0031] In various applications as illustrated herein, it is beneficial to form the antenna on a flexible substrate. Flexible substrates include kapton™ polyimide substrate and other similar substrates known in the art.
[0032] FIG. 2 shows a Vivaldi-Monopole antenna in accordance with another embodiment. The antenna is similar to the embodiment described above. However, the antenna in this embodiment comprises three conductor portions 207 a; 207 b; and 207 c, respectively. The first conductor portion 207 a is separated from the second conductor portion 207 b by the first slot 110 of the tapered slot element 205 extending therebetween, and by a first gap 203 extending therebetween at the rear edge. The third conductor portion 207 c forming the monopole element 206 , is separated from the second conductor portion 207 b by a second gap 201 extending therebetween at the front edge.
[0033] In this form, the Vivaldi-Monopole antenna can be tailored to various applications by coupling a component between two adjacent conductor portions. For example, a low pass filter 204 can be coupled between the first conductor portion 207 a and the second conductor portion 207 b across the first gap 203 . Moreover, a high pass filter 202 can be coupled between the second conductor portion 207 b and the third conductor portion 207 c across the second gap 201 . In this regard, the respective conductor portions can be filtered for configuring the Vivaldi-Monopole antenna for various resonances depending on the application. If filtering is not desired, a conductor, resistor or other passive component may be coupled between two adjacent portions.
[0034] FIG. 3 shows a sectional view 300 of the Vivaldi-Monopole antenna in accordance with an embodiment. The antenna comprises a substrate layer 304 having a top surface and a bottom surface thereof. A metallized layer 303 , preferably copper, tin, gold, or other conductor metal, is disposed about the top surface of the substrate. A layer of solder mask 301 is applied to the metallized layer in a desirable pattern as would be determined by those having skill in the art. An optional conductive layer 302 , for example, tin, can be formed on a portion of the metallized layer 303 to form one or more solder pads. A bottom solder mask layer 307 is formed on the bottom surface of the substrate. An adhesive layer 306 is formed below the bottom solder mask layer. A removable liner 305 is attached to the adhesive layer.
[0035] Although the Vivaldi-Monopole antenna can be fabricated in a rigid form, it is preferable to form the antenna on a flexible substrate for certain applications.
[0036] For example, FIG. 4A shows a device housing 405 having an orthogonal bend (or right-angle) corner. In order to attach the antenna 404 at the corner, it is beneficial to form the antenna on a flexible substrate.
[0037] Similarly, FIG. 4B illustrates a wavy device housing. A flexible antenna 402 can conform to the wavy housing 403 .
[0038] An example of an application suitable for a flexible Vivaldi-Monopole antenna is a utility meter, such as an electric or water utility meter. FIG. 4C illustrates the flexible antenna 400 attached to a round utility meter housing 401 .
[0039] FIG. 5 shows a plot of return loss (dB) of the Vivaldi-Monopole antenna of FIG. 1 over a wideband spectrum. Both a simulated plot and a measured plot are illustrated.
[0040] FIG. 6 shows a plot of efficiency (%) of the Vivaldi-Monopole antenna of FIG. 1 over a wideband spectrum.
[0041] FIG. 7 shows a plot of peak gain (dB) of the Vivaldi-Monopole antenna of FIG. 1 over a wideband spectrum.
[0042] FIG. 8A illustrates the current distribution of the Vivaldi-Monopole antenna according to the embodiment of FIG. 1 for a first working frequency at 700 MHz.
[0043] FIG. 8B illustrates the current distribution of the Vivaldi-Monopole antenna according to the embodiment of FIG. 1 for a first working frequency at 3000 MHz.
[0044] Although the above examples illustrate particular embodiments, it should be understood by those having skill in the art that a variety of alternative embodiments can be practiced with little experimentation or deviation from these examples. Accordingly, the spirit and scope of the invention shall not be limited to these descriptions, which are provided as illustrative examples of the various features and embodiments only, but rather, the scope shall be set forth by the appended claims.
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A Vivaldi-Monopole antenna is a small form ultra-wideband antenna configured for low frequency operation in modern wireless devices. The Vivaldi-Monopole antenna comprises a tapered-slot element and a monopole element, wherein current modes of each element are combined to yield a functional and small form ultra-wideband antenna configured for low frequency resonances.
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TECHNICAL FIELD
[0001] The present invention relates to medicinal mushrooms, more particularly to species of genera Coprinus and Tremella mushrooms and to new and distinct strains of higher Basidiomycetes designated Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296. The invention further relates to fruiting bodies, submerged cultivated mycelial or single cell biomass and extracts from these new strains comprising various biologically active compounds, and their use as human and animal dietary supplements, prebiotics, cosmeceuticals, and in the therapy of several diseases and conditions, as well as anti-phytoviral agents.
BACKGROUND ART
[0002] Mushroom biotechnological products have multibeneficial effects to human welfare, e.g., as food, health tonics and medicine, feed and fertilizers, and to protect and regenerate the environment. Pharmaceutical substances with potent and unique health-enhancing properties were isolated recently from medicinal mushrooms and distributed worldwide. Many of them are pharmaceutical products, while others represent a novel class of dietary supplements or “mushroom nutraceuticals” or “nutriceuticals”, mycochemicals, phytochemicals, and designer food. Several antitumor polysaccharides, such as hetero-β-glucans and their protein complexes (e.g., xyloglucans, and acidic β-glucan containing uronic acid) as well as dietary fiber, lectins, and triterpenoids, have been isolated from medicinal mushrooms.
[0003] Higher Basidiomycetes mushrooms contain a large amount of polysaccharides, especially different types of β-glucans. The anti-tumor effects of β-glucans seem to be related to their molecular weight and solubility. Only the low-molecular weight lentinan, for example, shows high anti-tumor activity. Unsurprisingly, soluble β-glucans appear to be stronger immunostimulators than insoluble ones.
[0004] Submerged cultivated one-cell biomass and fruiting bodies, of some species of genus Tremella , especially strains of T. mesenterica contain high levels of glucuronoxylomannan and β-glucans, and both the biomass and the purified polysaccharides have been shown to possess hypoglycemic and hypotrygliceridic activity (U.S. Pat. No. 6,383,799; U.S. Pat. No. 6,362,397).
[0005] Higher Basidiomycetes mushrooms contain a large amount of polysaccharides, proteins, well-balanced essential amino acids, melanins, lipids comprising essential fatty acids, triterpenoids, antioxidant agents, vitamins, and other biological active substances. Also, dietary fibers belonging to glucans, chitin, and heteropolysaccharides including pectinous substances, hemi-celluloses or polyuronides, are abundant in the tissue of all mushrooms, which are capable of absorbing bile acids or hazardous materials in the intestine, and thus can act as carcinostatics and decrease various kinds of poisoning.
[0006] In addition, fungal substances are known as: (i) modulators of NF-κB activation pathway that plays critical roles in a variety of physiological and pathological processes; (ii) antioxidant suitable as supplements in the human diet for preventing or reducing oxidative damage caused by oxidative stress reactions; (iii) immunomodulators; and to affect inflammatory processes.
SUMMARY OF INVENTION
[0007] The present invention is directed to new and distinct varieties of higher
[0008] Basidiomycetes mushroom selected from Coprinus comatus HAI-1237 deposited under The Budapest Treaty with the Centralbureau voor Schimmelcultures (CBS) under Accession No. CBS 123401 (hereinafter Coprinus comatus CBS 123401), and Tremella mesenterica HAI-17 deposited under The Budapest Treaty with the Centralbureau voor Schimmelcultures (CBS) under Accession No. CBS 123296 (hereinafter Tremella mesenterica CBS 123296).
[0009] In other aspects, the present invention relates to the biomass of the mushrooms of the invention rich in nutraceutical agents and biologically active substances including carbohydrates, proteins rich in essential amino acids, vitamins, lipids rich in essential fatty acids, antioxidant agents and minerals. The biomass can be obtained from the fruiting body or the mycelium of Coprinus comatus CBS 123401 or the mycelium of Tremella mesenterica CBS 123296. The mycelial culture of Tremella mesenterica CBS 123296 is in the form of one-cell biomass.
[0010] In a further aspect, the present invention relates to extracts from the mushrooms of the inventions having nutraceutical and biological activity. The extracts can be obtained from the mycelium or the fruiting body of the mushrooms.
[0011] In still other aspects, the invention relates to novel carbohydrates isolated from the extracts, compositions comprising the biomass or extract from the mushrooms of the invention or the novel carbohydrates isolated from the extracts, to natural food supplement, pharmaceutical, prebiotic, nutraceutical, beverage or cosmetic products comprising a composition of the invention, to a pharmaceutical composition comprising a pharmaceutically acceptable carrier and an active ingredient selected from a composition of the invention and one of the novel carbohydrates, and to processes for producing the biomass and extracts.
BRIEF DESCRIPTION OF DRAWINGS
[0012] FIG. 1 depicts a scheme of the general methodology for the production of submerged cultured mycelium of Coprinus comatus or Tremella mesenterica in fermentor or in bioreactor technology: a—preparation of standard agar media for Petri dish; b—spores or parts of fruiting body which are used for preparation of culture; c—culture on Petri dish; d—museum culture on agar slant in tube; e—microscopic examination of museum culture; f—pre-inoculums culture in 250 mL Erlenmeyer flask; g—homogenization of pre-inoculums culture; h—cultivation of homogenized mycelial biomass in 2 L Erlenmeyer flasks; i—homogenization of mycelial biomass for inoculation fermentor medium; j—growth medium for fermentor; k—cultivation of mycelial biomass in fermentor; l— harvest of mycelial biomass; m—dried biomass formulations for dietary supplements (DS), pharmaceuticals and other products; HM, Harvest Mycelia;
[0013] FIG. 2 shows effect of E1 and E2 extracts on pIκBα levels as determined by Western immunoblot. The figure is representative of two independent experiments with similar results. E1—Cultural liquid (water) extract; E2—Ethyl acetate extract.
[0014] FIG. 3 displays densitometric analysis of the Western immunoblot of FIG. 2 showing the effects of E1 and E2 extracts on pIκBα compared to 100 μM H 2 O 2 effect. (Results are presented as folds of two independent experiments to the mean of only H 2 O 2 -treatments±standard deviation).
[0015] FIG. 4 shows IKKβ inhibition activity of Coprinus comatus extracts E1 and E2. Extracts E1 and E2 (100 and 200 μg/ml) and 600 nM of the IKK-β inhibitor Fuct (1 μM) were incubated with 100 ng of GST-IκBα substrate and 5 ng of IKK-β enzyme, and tested for their ability to inhibit IKK-β activity using an ELISA-based kinase activity assay as described in Materials and Methods. E1—crude cultural liquid (water) extract; E2—crude ethyl acetate extract.
[0016] FIG. 5 depicts 1 H NMR spectrum of the Coprinus water extract.
[0017] FIGS. 6A-D show Gas Chromatography (GC) analysis of monosaccharide content of the whole cells, extracts, and residues after extraction. (A) Water extract; (B) Whole cells; (C) Cells after water extraction; and (D) Cells after NaOH extraction.
[0018] FIG. 7 depticts a size-separation chromatogram of polysaccharides from water and NaOH extracts of Coprinus comatus , partially separated by size-exclusion chromatography on Sephadex G-50.
[0019] FIGS. 8A-B show methylation analysis of β-glucan extracted from Ganoderma sp. (A) and Coprinus comatus CBS 123401 (B).
[0020] FIG. 9 depicts a GC trace of methylated sugars obtained from β-glucan isolated from Tremella mesenterica CBS 123296.
[0021] FIG. 10 show GC traces of methylated sugars obtained from the newly isolated strain of Tremella mesenterica CBS 123296 (A) and pure glucuronoxylomannan (B).
[0022] FIG. 11 shows the effect of GXM (1000 μg/mL) on perceptivity of the tobacco plant of variety Immune 580 relative to Tobacco Mosaic Virus (TMV). Abscissa: interval between introduction of GXM and inoculation of TMV (days). Ordinate: the ratio (%) of the number of local lesions in the experiment (dark solid bars) and in control (textured light bars).
[0023] FIG. 12 shows the influence of GXM (2500 μg/ml) on perceptivity of the Nicotiana tabacum plant of variety Immune 580 relative to TMV. Abscissa: interval between introduction of GXM and inoculation of TMV (days). Ordinate: the ratio (%) of the number of local lesions in the experiment (dark solid bars) and in control (textured light bars).
[0024] FIG. 13 shows the influence of GXM (2500 μg/ml) on the growth of local lesions, induced by TMV in the Nicotiana tabacum plant of variety Immune 580. Abscissa: interval between introduction of GXM and inoculation of TMV (days). Ordinate: size of local lesions (mm) in the experiment (dark solid bars) and in control (textured light bars).
[0025] FIG. 14 shows the influence of actinomycin D (AMD) on induced GXM resistance in Nicotiana tabacum plants of variety Immune 580 inoculated with TMV. Abscissa: variants of the experiment: 1—GXM; 2—mixture of GXM and AMD (10 μg/mL); 3—AMD (10 μg/mL) introduced 2 days after GXM; 4—AMD (20 μg/mL) introduced 2 days after GXM; 5—AMD (10 μg/mL). Ordinate: the ratio (%) of the quantity of local lesions in the experiment (dark solid bars) and in control (textured light bars).
DETAILED DESCRIPTION OF THE INVENTION
[0026] In one aspect, the present invention relates to a biomass of the Basidiomycetes mushrooms Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296 rich in nutraceutical agents and biologically active compounds including proteins rich in essential amino acids and carbohydrates and further comprising vitamins, lipids rich in essential fatty acids, antioxidant agents, and minerals.
[0027] In one embodiment, the biomass is obtained from the fruiting body or the mycelium of Coprinus comatus CBS 123401 or the mycelium of Tremella mesenterica CBS 123296 in the form of single-cell biomass, for example by cultivation of the strain in submerged culture on nutrient media.
[0028] The invention further relates to pure submerged mycelial cultures of Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296, wherein the mycelial culture of Tremella mesenterica CBS 123296 is in the form of single-cell biomass. The fact that the Tremella mesenterica mycelial culture grows as a unicellular organism, like yeast, provides for a very high growth rate and biomass productivity which is the highest among all Basidiomycetes mushrooms, reaching up to 27 g of dried biomass per liter of media.
[0029] The chemical composition of mycelium of the two mushrooms of the invention was determined as shown in Examples 4 and 7. Many of the constituents shown herein to be present in the mushrooms of the present invention have multiple beneficial properties such as anti-cancer activity, immunomodulating activity, anti-glycemic, anti-diabetic and insecticidal activity.
[0030] The mycelial biomass of Coprinus comatus CBS 123401 has about 39% carbohydrates and about 37% proteins, and that of Tremella mesenterica CBS 123296 has about 54% carbohydrates and about 20% proteins of the dry weight of mycelium. Submerged culturing of mushroom polysaccharide producers allows the production under controlled conditions of a constant composition in a short time period using culture medium of defined composition.
[0031] The carbohydrates in the biomass include both polysaccharides and di- and mono-saccharides. Examples of polysaccharides of the biomass of Coprinus comatus CBS 123401 include β-glucans, preferably a low molecular weight water-soluble β-glucan, and galactans, preferably neutral fucogalactan.
[0032] Thus, the present invention relates to a novel low molecular weight water-soluble β-glucan composed of a backbone structure of β-1-3-linked D-glucose residues bearing, at some of the 6-positions, side chains of β-1-6-D-glucose residues as shown in Example 4.2 herein. The β-glucan is obtained from Coprinus comatus , preferably Coprinus comatus CBS 123401, and has a molecular weight of less than 10,000 Da, preferably about 1000 to about 10,000 Da.
[0033] Examples of polysaccharides of the biomass of Tremella mesenterica CBS 123296 include β-glucans, preferably a linear 3,4 β-glucan, and glucuronoxylomannan. Thus, the present invention further relates to a novel water insoluble linear 3,4 β-glucan and to a glucuronoxylomannan obtained from Tremella mesenterica CBS 123296 as shown in Example 7.4 herein. The glucuronoxylomannan consists of a linear backbone of α-(1→3)-linked mannan, glycolized by β-(1→2)(1→4)-linked oligosaccharides of xylose and glucuronic acid, which bestowes polyanion properties, and may by used as an anti-glycemic and anti-diabetic agent.
[0034] The β-glucans of the present invention have antitumor and immunomodulating, particularly immunostimulatory activities, and the glucuronoxylomannan of the present invention has hypoglycemic, immunostimulating, and hypocholesterolemic activities and are promising as a herbal medicine to prevent and treat diseases and conditions in which strengthening of the immune system is important, such as to prevent and treat diabetes, cancer, viral diseases such as AIDS, heart diseases, blood pressure, and as hypocholesterolemic agents to treat high cholesterol conditions. Polysaccharides of both species can be a source of new prebiotics. A “prebiotic agent” is defined herein as a selectively fermented ingredient that allows specific changes, both in the composition and/or activity, in the gastrointestinal microflora that confers benefits upon host well-being and health. Chitin, also present in the biomass, is an important constituent of dietary fibers.
[0035] The mono- and di-saccharides found in the mycelial biomass include glucose arabinose, xylose, mannose, galactose, glucosamine and trehalose. All these mono- and di-saccharides are important for the health. In addition, mannose has been shown to prevent the adhesion of bacteria to tissues of the urinary tract and bladder, and glucosamine is known as useful for treatment of osteoarthritis and to rebuild cartilage.
[0036] The mycelial biomass proteins of the mushrooms of the present invention are rich in glutamic acid, aspartic acid, leucine, cystein, methionine, threonine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine and histidine. C. comatus further contains γ-aminobutyric acid. Thus, the proteins of mycelium contain 10 out of the 11 essential amino acids; threonine, valine, isoleucine, leucine, histidine, lysine, methionine, cysteine, phenylalanine, tryptophan and tyrosine. The biomass of the present invention therefore constitutes an important dietary supplement due to the presence of the proteins rich in essential amino acids.
[0037] The biomass of Coprinus comatus CBS 123401 comprises the vitamins: A, B 1 , B 2 , B 3 , C, and E; and the biomass of Tremella mesenterica CBS 123296 comprises the vitamins: A, B 1 , B 2 , B 3 , B 6 , B 7 , C, and E. Thus, the biomass and extracts of the mushrooms of the present invention containing high levels of important vitamins serve as an excellent source of vitamins and may be used as nutraceuticals and/or may be added to food and beverage products as dietary supplements.
[0038] The mycelial biomass of Coprinus comatus CBS 123401 further comprises lipids including the fatty acids pentadecanoic, palmitic, palmitoleic, heptadecanoic, stearic, oleic, linoleic (C18:2n6), α-linolenic (C18:3n3), γ-linolenic (C18:3n6), arachidic, heneicosanoic, behenic, and lignoceric acids; and the biomass of Tremella mesenterica CBS 123296 comprises the fatty acids oleic acid-(C18:1), linoleic acid (C18:2n6), palmitic acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0) and myristic acid. The fatty acids are found in the mushroom in the form of their esters with glycerol. A high nutritional quality of the mushroom is made evident by the presence of the essential unsaturated fatty acids α-linolenic acid (C18:3n3) and linoleic acid (C18:2n6). The latter gives rise to the omega-6 series of polyunsaturated fatty acids, which incorporation into phospholipids affect cell membrane properties such as fluidity, flexibility, permeability and the activity of membrane bound enzymes.
[0039] The mycelial biomass of the mushrooms of the invention comprises also minerals, both macroelements and microelements, including aluminum, copper, iron, potassium, magnesium, manganese, phosphorus, silicon, sodium, titanium and zinc. A daily dose of biomass of either one of the two mushrooms of the present invention endows an excellent source of iron and other minerals.
[0040] It has also been found in accordance with the present invention that the mycelial and biomass of the Coprinus comatus CBS 123401 strain of the invention comprise anti-oxidant agents, free-radical scavenging agents, melanin (confers protection against photo-aging of the skin, particularly protects the skin from solar UV radiation, and also protects against damage to internal organs caused by ionizing radiation, and may serve to sequester potentially toxic metal ions through its carboxylate and phenolic hydroxyl groups) and lectins (see Example 4.3), in particular lactose, galactose and glucosamine binding lectins, which can be useful in assays involving the identification of sugar moieties of polysaccharides and glycoproteins.
[0041] The biomass of the mushrooms of the present invention may be further used in prebiotic or nutraceutical compositions. A “mushroom nutraceutical” is defined as a refined or partially refined extract or dried biomass from either the mycelium or the fruiting body of the mushroom, which is consumed in the form of capsules or tablets as a dietary supplement (not a conventional food) and which has potential therapeutic applications. Regular intake may enhance the immune responses of the human body, thereby increasing resistance to disease, and in some cases causing regression of a disease state.
[0042] In another aspect, the present invention provides extracts of the mushrooms of the invention having nutraceutical and biological activities. In one embodiment, the extract is from Coprinus comatus CBS 123401. In another embodiment extract is from Tremella mesenterica CBS 123296. The extracts are obtained from the fruiting body or the mycelium of Coprinus comatus CBS 123401 or from the mycelium of Tremella mesenterica CBS 123296. In a preferred embodiment, the extracts of the mushrooms of the invention are obtained from a pure submerged mycelium culture.
[0043] The extract obtained from Coprinus comatus CBS 123401 culture is enriched in a low molecular weight water-soluble β-glucan and/or galactans, preferably neutral fucogalactan, and the extract obtained from Tremella mesenterica CBS 123296 culture, is enriched in a linear 3,4 β-glucan and/or glucuronoxylomannan, which has anti-glycemic and anti-diabetic activity.
[0044] In one embodiment, the biological activity present in the extract of the mushrooms of the present invention is NF-κB pathway modulating activity, anti-oxidant activity, free radical scavenging activity, anti-radiation activity, metal ion scavenging activity, interferonogenous activity, immunomodulating activity, anti-glycemic activity, anti-diabetic activity, hypocholesterolemic activity, anti-allergic activity, anti-parasitic activity, insecticidal activity and/or anti-plant viral activity.
[0045] The terms “interferonogenous activity” and “interferonogenous agent” as used herein refer to an activity or agent that increase the concentration of interferon in the blood plasma of a mammal.
[0046] The terms “immunomodulating activity” and “immunomodulating agent” as used herein refer to, but are not limited to, mitogenicity, stimulation of hematopoietic stem cells, activation of alternative complement pathway, and activation of immune cells such as T H cells, Tc cells, B cells, macrophages, dendritic cells, and natural killer (NK) cells.
[0047] The terms “anti-glycemic activity” and “anti-glycemic agent” refer to an activity or agent that reduces blood glucose level, while the terms “anti-diabetic activity” and “anti-diabetic agent” refer to an activity or agent that treats diabetes mellitus by lowering glucose levels in the blood.
[0048] The insecticidal activity involves attracting social insects such as carpenter ants, fire ants, coptotermes , Formosan termites and reticulitermes termites and infecting and killing these insects.
[0049] In particular, and as is shown herein below in the Examples, Coprinus comatus CBS 123401 ethyl acetate extract has NF-κB pathway modulating activity (Example 3), and anti-oxidant activity and/or free radical scavenging (Example 2). Such an extract may be useful in treatment of an NF-κB-dependent disease such as, but not limited to, cancer, immunological disorders, septic shock, transplant rejection, radiation damage, reperfusion injuries after ischemia, arteriosclerosis and neurodegenerative diseases.
[0050] The extract obtained from Tremella mesenterica CBS 123296 culture comprises glucuronoxylomannan and therefore has anti-diabetic activity, and further comprises immunomodulating activity, for example such activity that causes an increase of functional reserve of macrophages, and interferrouneus activity (see Example 8) and/or anti-plant viral activity (see Example 9). The term “functional activity” as used herein refers to the difference between the spontaneous and stimulated (NBT-tests) activity indices, i.e. the activity of a phagocytotic cell, such as a macrophage, at its resting state as compared with its activity following activation by for example exposure to a pathogenic bacterium.
[0051] In still another aspect, the present invention relates to a composition comprising a biomass or extract according to the present invention. In certain embodiments, the composition comprises a mixture of biomasses obtained from Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296, or a mixture of extracts obtained from Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296. In one embodiment, the composition comprises a biomass rich in nutraceutical agents and biologically active substances obtained from the mycelium or from the fruiting body of Coprinus comatus CBS 123401, or an extract of said biomass. In another embodiment the composition comprises a biomass rich in nutraceutical agents and biologically active substances obtained from the mycelium of Tremella mesenterica CBS 123296, or an extract of said biomass.
[0052] In still yet another aspect, the present invention relates to a composition comprising a carbohydrate selected from the low molecular weight water-soluble β-glucan, the water insoluble linear 3,4 β-glucan, the glucuronoxylomannan, all of which as defined herein above and in the Examples herein below, or a combination of at least two of these carbohydrates. In view of the above, the present invention provides, in an additional aspect, natural food supplement, prebiotic, nutraceutical, beverage and cosmetic products comprising a composition of the present invention. The present invention further provides pet food, insecticidal, anti-parasitic and anti-plant virus products, comprising a composition of the present invention.
[0053] In yet an additional aspect, the present invention provides a pharmaceutical composition comprising a pharmaceutically acceptable carrier and an active ingredient selected from (a) a composition of the present invention; (b) the low molecular weight water-soluble β-glucan; (c) the water insoluble linear 3,4 β-glucan; (d) the glucuronoxylomannan; all of which as defined herein above and in the Examples herein below; or (e) a combination of at least two of the active ingredients of (b) to (d).
[0054] In certain embodiments, the natural food supplement, prebiotic or a nutraceutical product and the pharmaceutical compositions of the present invention may be used for (a) treating diabetes or reducing blood glucose levels; (b) inducing an immunomodulatory response; or (c) reducing blood cholesterol levels or reducing the build up of cholesterol.
[0055] The natural food supplement, prebiotic or nutraceutical product, or a pharmaceutical composition of the present invention may be administered alone or in combination with an anti-cancer drug, to a cancer patient in order to induce an immunostimulatory response for treating cancer.
[0056] The term “treating” as used herein refers to the alleviation, reduction of progression or complete cure of the disease or disorder, or to the reduction of symptoms related to or caused by the disease or disorder.
[0057] The pharmaceutical compositions for use in accordance with the present invention may be formulated in conventional manner using one or more pharmaceutically acceptable carriers comprising excipients and auxiliaries. Techniques for formulation and administration of drugs may be found, for example, in “Remington's Pharmaceutical Sciences”, Mack Publishing Co., Easton, Pa., latest edition.
[0058] The pharmaceutical compositions of the present invention are formulated for systemic administration by any suitable route, for example, for oral delivery, parenteral delivery including intramuscular, intravenous, subcutaneous, intrathecal, or intraperitoneal injection, or for local administration by topical drug delivery.
[0059] For any composition for use in the method of the invention, the therapeutically effective amount or dose can be estimated initially from in-vitro and cell culture assays. For example, a dose can be formulated in animal models to achieve a desired concentration or titer. Such information can be used to more accurately determine useful doses in humans.
[0060] In still an additional aspect, the present invention relates to an agricultural composition comprising an agricultural carrier and an active ingredient selected from a composition of the present invention or the glucuronoxylomannan as defined herein. In certain embodiments, the agricultural composition is for inducing resistance in plants to a plant pathogen, such as a plant virus.
[0061] In one embodiment, the plant-virus is a plant virus capable of inducing a hypersensitive response in the infected plant, e.g. plant viruses including Tobacco mosaic virus and other Tobamoviruses, such as tomato mosaic virus, pepper green mottle virus and ondontoglossum ringspot virus. In certain embodiments, the virus is Tobacco mosaic virus.
[0062] The agricultural compositions of the invention may further comprise inert additives. Such additives include thickeners, flow enhancers, wetting agents, antifoaming agents, buffers, lubricants, fillers, drift control agents, deposition enhancers, adjuvants, evaporation retardants, frost protecting agents, insect attracting odor agents, UV protecting agents, fragrances, and the like. The thickener may be a compound that is soluble or able to swell in water, such as, for example, polysaccharides of xanthans (e.g., anionic heteropolysaccharides), alignates, guars or celluloses; synthetic macromolecules, such as polyethylene glycols, polyvinyl pyrrolidones, polyvinyl alcohols, polycarboxylates of swellable structure-forming silicates such as pyrogenic or precipitated silicic acids, bentonites, montmorillonites, hectonites, or attapulgites; or organic derivatives of aluminum silicates. The frost protecting agent may be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. The antifoaming agent may be, for example, a polydimethylsiloxane. The agricultural composition may also comprise surfactant systems adapted to water- or oil-based products, as is commonly known in the art.
[0063] The present invention further provides a process for producing an extract from the mushrooms of the present invention having biological activity, wherein the biological activity is NF-κB pathway modulating activity, anti-oxidant activity, free radical scavenging activity, anti-radiation activity, metal ion scavenging activity, interferonogenous, immunomodulating, anti-glycemic, anti-diabetic, hypocholesterolemic activity, anti-allergic activity, anti-parasitic activity, or anti-plant viral activity, said process comprising: cultivating the fungi Coprinus comatus CBS 123401 or Tremella mesenterica CBS 123296 in submerged culture in nutrient media, isolating the resulting biomass of edible fungi from the culture broth, drying and grinding said biomass into fine powder which is subjected to solvent extraction and freeze drying. In particular, the process is for producing an extract of Tremella mesenterica , preferably Tremella mesenterica CBS 123296, enriched in glucuronoxylomannan.
[0064] A further process is provided for producing a biomass from the mushrooms of the present invention which is rich in polysaccharides, monosaccharides, proteins, essential amino acids, vitamins, essential fatty acids, minerals and microelements, said process comprising: cultivating said mushrooms in submerged culture on nutrient media, isolating the resulting biomass of edible fungi from the culture broth, and drying and grinding said biomass into fine powder.
[0065] Of particular importance is the further process provided by the present invention for cultivating on nutrient media a single cell submerged culture of a mushroom comprising the genus Tremella selected from Tremella mesenterica, Tremella fuciformis , and Tremella aurantia , preferable Tremella mesenterica CBS 123296.
[0066] It has been found in accordance with the present invention that the nutrient media used for cultivating Coprinus comatus for the purpose of the processes defined above should be of the following composition (g/L of distilled water): glucose, 15; peptone, 3; yeast extract, 5; KH 2 PO 4 , 0.8; K 2 HPO 4 , 0.2; MgSO 4 .7H 2 O, 0.5; and the nutrient media used for cultivating Tremella mesenterica for the purpose of the processes defined above is of the following composition (g/L of distilled water): Sucrose, 50; yeast extract, 0.5; KCl, 1; Mg acetate.4H 2 O, 1.0; NaH 2 PO 4 .H 2 O, 0.5; Na 2 HPO 4 .7H 2 O, 1.0.
[0067] The invention will now be illustrated by the following non-limiting Examples.
EXAMPLES
Materials and Methods
[0068] 1. Submerged Cultivation of Mycelial Biomass of Coprinus comatus in Erlenmeyer Flasks and Fermentor
[0069] FIG. 1 shows the general methodology for the production of submerged cultured mycelium of Coprinus comatus CBS 123401 and Tremella mesenterica CBS 123296 using fermentor or bioreactor technology.
[0070] The general scheme of mushroom submerged culture mycelium (SCM) production includes 5 steps of culture growth:
[0071] Museum culture (I)->Intermediate culture (II)->Pre-inoculums culture (III)->Inoculums culture (IV)->Fermentation culture (V).
[0072] Three types of culture media are used for SCM production: standard agar medium (steps I and II), liquid standard inoculums medium (steps III and IV), and fermentation medium (step V). Museum cultures are, developed on agar slants in tubes; intermediate cultures are developed on agar slants in tubes or Petri dishes. Pre-inoculums and inoculums cultures are developed in Erlenmeyer flasks using a rotary shaker. Fermentation cultures are developed in fermentor Bioflo 2000 (New Brunswick Scientific, USA) that is equipped with instrumentation for the measurement and/or control of agitation, temperature, pH, dissolved oxygen concentration (pO 2 ), and foam.
[0073] For the first pre-inoculums culture, 250 ml Erlenmeyer flask is inoculated by one to three week old mushroom mycelium from the Petri dish. Five-to-six pieces (5-7 mm in diameter) from mycelium growing on the edge of the agar plate were transferred into the Erlenmeyer flask and cut on the flask wall into small pieces to increase the number of growth points of mycelia. Mycelium was inoculated in 250-mL Erlenmeyer flasks filled with 100 ml of defined synthetic medium. Fungal inocula were grown on synthetic medium consisting of the following components (g/L of distilled water): (g l −1 ): glucose, 15; peptone, 3.0; yeast extract, 5.0; KH 2 PO 4 , 0.8; K 2 HPO 4 , 0.2; MgSO 4 .7H 2 O, 0.5. Initial pH of the media was 6.0. Phosphate salts were sterilized separately (Sigma-Aldrich, St Louis, Mo., USA). The cultivation of inoculated flasks is carried out on a rotary shaker at 100 rpm and 27° C. for 6-7 days. At the end of cultivation, 1 ml of sample is taken from the culture for microscopic observation of culture purity.
[0074] For the second inoculums culture the biomass from the first pre-inoculums culture (pellets) was homogenized 2×30 seconds using a Waring Laboratory Blender (Waring, USA) and inoculated in a 2 L flask containing 700 mL of the same medium.
[0075] After 5-7 days of cultivation, mycelial biomass (pellets) were homogenized and used as inoculums culture for growth in a fermentor (Bioflo 2000 10 L, New Brunswick Scientific, USA) with 10 L of working volume on the same synthetic medium mentioned above. Initial parameters of cultivation were as follows: temperature 27° C.; pH—6.1; agitation—100 rpm, aeration—0.2 v/v/min. Antifoam used was polypropylene glycol 2000; 4% NaOH and 4% HCl were used to control pH.
[0000]
TABLE 1
Mycelial biomass production of Coprinus comatus CBS 123401 in
submerged culture as a function of time
Aeration,
Time, h
pH
DO, %
v/v/min
RPM
Biomass, g/l
0
6.14
100
0.2
100
0.2
24
5.8
28
0.2
100→200
0.8
48
5.8→6.0
19
0.2→0.4
300
3.5
72
6.0
17
0.4→0.5
300
5.0
96
6.0
14
0.5
300
6.9
120
6.0
18
0.5
300
7.5
144
6.0
20
0.5
300
8.4
168
6.0
22
0.5
300
9.3
DO, dissolved oxygen
[0076] Initially, pH of the medium was not controlled. However, when it decreased to 5.2, the pH was kept constant automatically at the level of 6.0 to favor the fungus growth. After 24 h, the speed of agitation was increased to 200 rpm, then after 48 h to 300 rpm. After 48 h, the rate of aeration of the medium was increased to 0.4, then (after 72 h) to 0.5 v/v/min.
[0077] The maximal yield of mycelial biomass was 93 g/L of wet biomass or 9.3 g of dry biomass achieved on day 7 of fungus cultivation. The conditions of the cultivation are defined in Table 1. Vacuolated hyphae with clamp connections of mycelial biomass of Coprinus comatus CBS 123401 can be seen after 7 days of fungus cultivation (not shown).
[0000] 2. Evaluation of Coprinus comatus Antioxidant Activity
[0078] Biomass Estimation. After 8-11 days of C. comatus submerged cultivation, mycelial biomass was harvested with filtration and dried at 50° C. to a constant weight. The dried mycelia were milled to a powder form for extraction.
[0079] Antioxidant Extraction from C. comatus Biomass. Harvested mushroom mycelia were dried at 50° C. and milled to powders (4-10 g). Three different solvents (culture liquid instead of water, ethanol, and ethyl acetate) were used to extract antioxidant compounds from mushroom mycelia in ascending polarity. Although there were no literature data on the antioxidant presence in the culture liquid during Basidiomycetes cultivation, it is supposed that these mushrooms are capable to accumulate these compounds extracellularly. Therefore, to correctly evaluate the total antioxidant activity of screened mushrooms, it was decided to use proper culture liquids instead of water for the antioxidant extraction from the fungal biomasses.
[0080] In the first stage the mycelium was extracted for 3 h with culture liquid (1 g/10 ml) at 80° C. (using a water bath). After extraction, insoluble compounds were separated by centrifugation at 6000 rpm for 15 min and filtrated through the Wathman filter paper N 4. Filtrates were evaporated. The residues after centrifugation were then successively extracted on the rotary shaker at 150 rpm with ethanol (80%) at 27° C. and 3 h. After extraction the solutions were centrifuged, filtrated, and the organic solvents were evaporated from the extracts.
[0081] Antioxidants Extraction from Culture Liquid of Coprinus comatus CBS 123401. After biomass filtration, pH of the culture growth media was decreased to 2.0 using 96% sulphuric acid. One liter of growth medium per strain was separated 3 times with 500 ml of ethyl acetate, and the extract-solvent mixture was washed once with 0.5 l distilled water using a glass chemical separator. The extract-solvent mixtures were left in a chemical hood for solvent evaporation till a resin (or powder) was formed, which represented the actual crude fungal extract, collected in previously weighed 4 ml plastic tubes. All extracts were diluted with 99.9% dimethyl sulphoxide (DMSO) to the final concentration of 50 mg/ml, distributed into Eppendorf tubes, and kept at 70° C. prior to use.
Antioxidant Activity Assays
[0082] β-Carotene Bleaching Method. The antioxidant activity of C. comatus extracts was determined according to the β-carotene bleaching method. A reagent mixture containing 1 ml of (3-carotene (Sigma) solution (0.2 mg/ml in chloroform), 0.02 ml of linoleic acid (Sigma), and 0.2 ml of Tween 80 (Sigma) was evaporated to dryness under a nitrogen stream. Fifty milliliters of oxygenated distilled water and 0.2 ml of mushroom crude extracts (either ethanol or culture liquid) with different concentrations (2-8 mg/ml) were added. Pure methanol or water (0.2 ml) was used as the control, and the blank contained all the earlier chemicals except β-carotene. All these mixtures were then shaken to form a liposome solution and then incubated at 50° C. for 2 h. The absorbance of an aliquot (1 ml) of these liposome solutions at 470 nm was monitored by a spectrophotometer at time intervals of 20 min. Butylated hydroxyanisole (BHA) (Sigma) (2 mg/ml in methanol) was used as the standard. The bleaching rate (R) of f3-carotene was used as the standard. The bleaching rate (R) of 13-carotene was calculated according to
[0000] Equation (1)
[0000] R =ln( a/b )/ t Equation (1)
[0000] where: ln—natural log, a—absorbance at time 0, b—absorbance at time t, and t—incubation interval 20, 40, 60, 80, 100, or 120 min.
[0083] The antioxidant activity (AOA) was calculated, in terms of percent inhibition relative to the control, using Equation (2)
[0000] AOA=[( Rc control −R sample )/ R control ]×100 Equation (2)
[0084] Scavenging Activity on 1,1-diphenyl-2-picrylhydrazyl. The scavenging activity of extracts from C. comatus was measured on 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals. An aliquot of 0.5 ml of 0.1 mM DPPH radical (Sigma) in methanol was added to a test tube with 1 mL of mushroom ethanol or water extract of different concentrations (0.5 to 9 mg/mL). Methanol or water was used instead of the mushroom sample as a control. The reaction mixture was vortex-mixed at room temperature and the absorbance was determined immediately after mixing by measuring at 520 nm with a spectrophotometer. Inhibition of free radicals by DPPH was calculated as follows: I (%)=(A blank −A sample /A blank )×100, where I is inhibition (%), A blank is the absorbance of the control reaction (containing all reagents except the test compound), and A sample is the absorbance of the test compound. The extract concentration providing 50% inhibition (EC 50 ) was calculated from the graph of scavenging activity of radical percentage against extract concentration. Butylated hydroxyanisole (BHA) in concentration of 1 mg/ml methanol was used as the standard. Each value is expressed as mean±standard deviation (n=3).
[0000] 3. Study on Biological Activity of Extracts from Submerged Coprinus comatus
[0085] Cell Culture Preparation for the Experimental Work. All experimental work with cancer cell cultures was carried out in a sterile biological hood. Prior to each experiment, cells were trypsinized, collected, and counted in order to seed proper cell amounts according to the needs of the provided experiments.
[0086] MCF7 breast cancer cell culture normally grows attached to the flask bottom. In order to prepare these cells for use, the medium was discarded from the flask using disposable pipettes and 1-2 ml of trypsin was then added for 2-3 min. During trypsinization, cells were kept in a humidified incubator at 37° C. After cells detached from the flask bottom, in order to stop the trypsinization process, 5-10 ml of fresh medium was added, depending on the size of the flask used. Cells were mixed well via multiple pipetting, and 100 μl of the cell suspension were stained with 100 μl of 0.4% trypan blue solution, mixed well, and counted under microscope using a hemacytometer following the trypan blue exclusion method.
[0087] After establishing the available cell number, the cell suspension was additionally diluted and a certain number of cells were seeded according to the requirement of each experiment. Some cells were always kept in order to re-grow and sustain the available cell line for further experimental work. Stock suspensions of all cell lines were kept in liquid nitrogen and the experimental cell cultures were refreshed once every 2-3 months.
[0088] Cell Lysis, Preparation of Total Cell Lysates. In order to measure the intracellular levels of certain proteins as a response to the crude fungal extracttreatments, each time after cells were collected, a total cell lysis was performed. The exact procedure of the total cell lysis is described below.
[0089] Cells were collected and washed 3 times with cold phosphate buffered saline (PBS) through centrifugation for 5 min, at 3,000 rpm, and 4° C. The final cell amounts were collected in Eppendorf tubes and the left over PBS from the last washing was discarded so that only the cell pellet was left in each tube. For cell lysis, each time a freshly prepared lysis buffer was used with the following content: 500-1000 μL, depending on the number of samples, of cell lysis reagent, protease inhibitor cocktail, and both phosphatase inhibitor cocktails 1 and 2 at the final concentration of 1%, and 0.3 M of phenylmethylsulfonyl fluoride (PMSF). A lysis buffer 50 μL were added and samples were incubated for 30 min on ice with vigorous vortexing every 10 min, and final centrifugation for 10 min, at 13,000 rpm, and 4° C. The supernatants, representing the total cell lysate, were transferred to new Eppendorf tubes, and kept at −70° C., whereas the cell pellet were discarded. PIκBα-Kinetics According to H 2 O 2 -Stimulation. MCF7 breast cancer cells (2×10 5 ) were seeded in 5 ml of RPMI 1640 medium using 25 ml plastic flasks and maintained at 37° C. After 24 h, the growth medium was substituted with a medium containing 0.5% FCS in order to minimize the activation of signal transduction cascades by the growth factors presented in the serum. Twenty-four hours later, cells were supplemented with 50 or 100 μM H 2 O 2 for 5, 10, 20, 30, 40, and 60 min to detect inhibitory protein kappa B (IkBα) phosphorylation after H 2 O 2 stimulation in MCF7 breast cancer cell lines.
[0090] As a control, no H 2 O 2 treatment was used, according to which the kinetics of pIκBα were determined. Cells were collected, washed, and lysed as previously described. The experiments were performed in duplicates.
[0091] IKK Kinase Assay IκB kinase complex (IKK-β) activity was evaluated with IKK-β-inhibitor screening kit (Calbiochem, USA), an ELISA-based activity assay that utilizes a 50-amino acid GST-IkBαfusion polypeptide substrate that includes the Ser32 and Ser36 IKK-β phosphorylation sites. A hundred ng of the GST-IkBα substrate and 5 ng of recombinant IKK-β were incubated in the presence of 600 nM of the IKK-β inhibitor 5-(p-Fluorophenyl)-2-ureido]thiophene-3-carboxamide (Fuct), and 100 or 200 μg/ml of Coprinus comatus extracts. Reaction mixtures were added to wells precoated with glutathione to allow capture of GST-IkBα. The phosphorylated GST-IkBα substrate was detected using an anti-phospho-IκBα (Ser32/Ser36) antibody, followed by HRP-conjugation and color development with TMB substrate. The absorbance was monitored at 450 nm and is directly related to the level of IKK-β activity.
[0092] Densitometric Analysis. Densitometric quantitative analyses of the protein bands, detected by Western blot, have been carried out using the TotalLab software and are presented as folds of the volumes of protein bands. Densitometric analysis of the Western blots for pIκBα levels in response to the effects of the fungal extracts are presented as an average of the control values±SD.
[0000] 4. Content and Chemical Composition of Coprinus comatus
[0093] Analysis of the polysaccharide composition of Coprinus comatus CBS 123401 submerged cultivated mycelial biomass (10 g) were washed with boiling 96% ethanol (300 ml) for 2 h. The insoluble residue (8.2 g, 82%) was extracted with water (300 ml) in autoclave at 120° C. twice for 1 h. A small portion of the extract was dried and analyzed by NMR, the rest dialyzed, concentrated to 100 ml, ultracentrifuged at 120000 g for 3 h, solution treated with a few drops of bromine for decolorization (some protein precipitated after this and was removed by centrifugation), separated by gel chromatography on Sephadex G-50 to give 3 fractions (150, 220, and 130 mg), containing starch, β-glucan and galactan in various proportions. The insoluble residue (5.8 g) was extracted with boiling 5% KOH for 3 h, solution dialyzed and treated as above, to give protein-β-glucan mixture (300 mg).
[0094] Methylation analysis. Samples (1-3 mg) were dissolved in 1 ml dry DMSO at 100° C. Insoluble glucans were left overnight, and still were not completely dissolved. After cooling to room temperature powdered NaOH (˜30 mg) was added, mixture stirred for 30 min, 0.5 ml of MeI was added, strirring continued for 30 min, excess MeI removed by air stream, water (5 ml) was added. For soluble samples the product was extracted by CH 2 Cl 2 , washed with water, hydrolyzed with 3 M TFA (120°, 3 h), reduced with NaBD 4 , acetylated, analyzed by GC-MS. Insoluble compounds were recovered by dialysis and methylated one more time.
[0095] NMR experiments were carried out with a Varian INOVA 500 MHz spectrometer with a Varian Z gradient probe at 25° C. with acetone internal reference (2.225 ppm for 1 H and 31.5 ppm for 13 C) using standard pulse sequences DQCOSY, TOCSY (mixing time 120 ms), NOESY (mixing time 200 ms), HSQC and HMBC (100 ms long range transfer delay). Data processing was done with Bruker Topspin program.
[0096] Monosaccharide analysis. Samples (1-5 mg) were dissolved in concentrated HCl (0.2 ml) at 40° C. for 1 h, inositol standard (0.5 mg) was added, mixture diluted with water (0.4 ml) and heated at 100° C. for 2 h. Acid was evaporated under air stream, sugars reduced with NaBH 4 (10 mg, 30 min), AcOH (0.5 ml) was added, samples dried and then dried twice from MeOH (1 ml), acetylated with 0.5 ml of Ac 2 O, dried, analyzed by GC. This procedure gives improved recovery of glucose and glucosamine from insoluble polymers, but pentoses and 6-deoxyhexoses partly degrade. To get correct quantification of them, hydrolysis was performed with 3M TFA (120°, 3 h).
[0097] β-Glucan determination with Megazyme kit. General description: all glucans are solubilised in concentrated (37%; 10N) hydrochloric acid and then extensively hydrolysed by 1.3 N HCl at 100° C. for 2 h. Hydrolysis to D-glucose is completed by incubation with a mixture of highly purified exo-1,3-β-glucanase and β-glucosidase. The procedure was scaled down 10 times relative to the manufacturer instructions.
[0098] Measurement of total glucan (α-glucan+β-glucan) plus D-glucose in oligosaccharides, sucrose and free D-glucose. Glucans were extracted from samples (˜10 mg) with concentrated hydrochloric acid (0.2 ml) at 30° C. for 45 min with occasional vortex stirring. Acid was diluted 5 times with water and hydrolysis performed for 2 h at 100° C. Acid was neutralized with 1 ml of 2 M KOH, mixture diluted to 10 ml with 200 mM sodium acetate buffer (pH 5.0) and cleared by centrifugation at 1,500 g for 10 min. To 0.01 mL of the extract 0.1 ml of water and 0.1 ml of a mixture of exo-1,3-β-glucanase (20 U/mL) plus β-glucosidase (4 U/ml) in 200 mM sodium acetate buffer (pH 5.0) was added and mixture incubated at 40° C. for 60 min. 3.0 mL of glucose oxidase/peroxidase mixture (GOPOD) was added and incubated at 40° C. for 20 min. Absorbance at 510 nm was measured against the reagent blank.
[0099] Measurement of α-glucan (phytoglycogen and starch) plus glucose in sucrose and free d-glucose. Sample (10 mg) was extracted with 0.2 ml of 2 M KOH for 20 min with stirring. 0.8 mL of 1.2 M sodium acetate buffer (pH 3.8) was added followed by 0.02 mL of amyloglucosidase (1630 U/ml) plus invertase (500 U/mL) and incubated at 40° C. for 30 min with intermittent mixing. Samples diluted with water to 10 ml, cleared by centrifugation, 0.01 ml of sample was mixed with 0.01 ml of sodium acetate buffer (200 mM, pH 5.0) and 0.3 mL of GOPOD reagent and incubated at 40° C. for 20 min, absorbance at 510 nm was measured against the reagent blank. The reagent blank consists of 0.2 mL of sodium acetate buffer (200 mM, pH 5.0)+3.0 mL glucose oxidase/peroxidase reagent. The D-glucose standard consists of 0.1 mL D-glucose standard (1 mg/mL)+0.1 mL of sodium acetate buffer (200 mM, pH 5.0)+3.0 mL glucose oxidase/peroxidase reagent.
[0100] Extraction of Lectin Fraction from Submerged Cultivated Mycelium of Coprinus comatus CBS 123401.
[0101] Coprinus comatus mycelial biomass with a wet weight of 50 g were homogenized (⅙ w/v) under PBS (40 mM KH 2 PO 4 , 150 mM NaCl; pH 7.4) containing 1 mM phenylmethylsulfonyl fluoride. Homogenates were kept at 4° C. for 2 h and then centrifuged at 8000 g for 20 min. (NH 4 )SO 4 at 80% saturation was used for precipitation of protein fraction. Mixtures were allowed to stand overnight at 4° C. The precipitates were collected by centrifugation at 12000 g for 20 min, dissolved in a minimal volume of PBS, and dialyzed successively in distillate water and then in PBS. The resulting extract was analyzed for protein quantity, lectin activity, and sugar specificity.
[0102] Assay for hemagglutinating activity of lectin. To measure the lectin hemagglutinating activity a trypsinized erythrocyte suspension was used. The rabbit blood was collected in a 150 mM tri-sodium citrate buffer containing 150 mM NaCl. An erythrocyte suspension was freshly prepared by washing the erythrocytes three times with ten volumes of washing buffer (PBS). Next, trypsinization of 4% erythrocytes suspension was carried out at 37° C. for 1 h; then erythrocytes were washed and suspended in the same buffer as 2% suspension (v/v).
[0103] In the assay for lectin (hemagglutinating) activity, a serial two-fold dilution of the lectin solution in microtiter U-plates (50 μl) was mixed with 50 μl of a 2% suspension of rabbit red blood cells in PBS (pH 7.4) at 20° C. The results were recorded after 1 h. The hemagglutination titer, defined as the reciprocal of the highest dilution exhibiting hemagglutination, was equal to one hemagglutination unit. Specific activity is the number of hemagglutination units per mg of protein.
[0104] Sugar-binding specificity of lectins. The investigation of inhibition of lectin-induced hemagglutination by various carbohydrates was performed in a manner analogous to the hemagglutination test. Sugar samples (0.3 M) were prepared in phosphate buffered saline. All of the dilutions were mixed with an equal volume (25 μL) of a solution of the lectin. The mixture was allowed to stand for 30 min at room temperature and then mixed with 50 μL of 2% rabbit erythrocyte suspension. Sugar-binding specificity was expressed as the minimum concentration of each sugar required for inhibition of hemagglutination of titer 4 of the lectin. N-Acetyl-D-galactosamine (GalNAc); N-Acetyl-D-glucosamine (GlcNAc), D(+)Galactose (Gal); D(+)Glucose, D(+)Lactose (Lac); D(+)Mannose, xylose, cellobiose, and dulcitol were tested for detection of sugar-binding specificity of lectins.
[0000] 5. Characteristics of the Variety Tremella mesenterica CBS 123296; Submerged Cultivation of Single Cell Biomass in Erlenmeyer Flasks and Fermentor.
[0105] Preparation of cultures of Tremella mesenterica . Fruit bodies of Tremella mesenterica were collected in Israel on dead wood of Quercus sp. The basidiospore prints were obtained from a fresh fruit body situated under sterile Petri dish in a moist chamber with slowly decreasing humidity. Monosporous cultures were developed from basidiospore print spreading the spore suspension in sterile water onto the surface of malt agar in Petri dishes. Germinating basidiospores were investigated under stereomicroscope, and young colonies from yeast-like budding cells were transferred on to slants of malt agar (MA).
[0106] Inoculum of yeast-like haploid cells of Tremella mesenterica strains for the first step submerged culture was prepared as a suspension of 8-day old culture cells on MA slants in sterile water. A fermentation medium was inoculated by submerged culture, and a process for polysaccharide production was carried out in refrigerated orbital shaker at 220 rpm at a 27° C.
[0107] Polysaccharide production was estimated by alcohol precipitation of culture broth supernatant by 2 volumes of ethyl alcohol after separation cells of strain producer by centrifugation. A crude precipitate obtained from culture broth at the end of fermentation contains both extracellular polysaccharides and cells of strain producer.
[0108] A trace element mixture (micronutrients) composed of (g/l) 5.0 g/l FeSO 4 .7H 2 O; 0.625 g/l MnSO 4 .H 2 O; 0.435 g/l ZnSO 4 .7H 2 O and 0.2 g/l CuSO 4 .5H 2 O was prepared separately, and added to sterile culture media. The trace element mixture was added diluted 1:100 in culture medium to obtain a final cation concentration of (mg/l): Fe ++ -10.0; Mn ++ -2.0; Zn ++ -1.0; Cu ++ -0.5.
[0109] In order to prevent sediment formation of trace element hydroxides, pH of trace element solution is adjusted to 1.6-1.8 by 50% H 2 SO 4 prior to sterilization by autoclaving.
[0110] Culture media of determined composition were developed from peptone and yeast extract (Pronadisa), and mineral salts (Sigma).
[0000] 6. Content and Chemical Composition of Tremella mesenterica
[0111] Determination of acidic glucoronoxylomannan of Tremella mesenterica CBS 123296. Culture broth at the end of cultivation on fermentation medium was diluted three times in deionized water. Strain producer cells were separated by centrifugation for 10 min at 4° C. in an Eppendorf 5403 centrifuge at 5000 rpm. The supernatant was mixed with two volumes of ethyl alcohol, and crude polysaccharide was precipitated. The mixture of polysaccharides precipitated from culture broth was dissolved in water, and passed through a chromatography glass column filled with Amberlite IR-120 (H + -form). Acidic glucoronoxylomannan was precipitated from the collected fraction by gradual addition of 10% aqueous cetyl pyridinium chloride (CPC) until no more precipitate was formed. The insoluble CPC complex was collected by centrifugation, and dissolved into 10% sodium chloride. After separation of insoluble particles by centrifugation, the acidic polysaccharide was precipitated by addition of two volumes of ethanol.
[0112] The purified polysaccharide was obtained by dissolving the precipitate in water, followed by repeated precipitation with alcohol.
[0000] 7. Interferonogenous and Immuno-Modulating Properties of Tremella mesenterica Preparations.
[0113] Determination of IFN level in blood plasma and functional activity of phagocytic cells The IFN level in the blood plasma was estimated by the oppression of the cytopathic influence of a test-virus (virus of vesicular stomatitis, Indiana strain—VSV) in the culture of mice fibroblasts cells L-929. Alveola of 96-alveola culture panel were filled with 100 μl of cell suspension (1×10 6 cells/mL) and incubated for 18 hours at 37° C. in the atmosphere of 5% CO 2 , then 100 μL of the double-diluted test samples were added. After 18 hours 50 μL of previously titrated work-dilute of VSV were added. The panels were incubated under the same conditions. The results were evaluated under microscope. The reciprocal of the final IFN dilution, which provided 50% cells-protection against cytopathic influence of the test-virus, was assumed as the IFN activity unit. The IFN titre was expressed in units/ml.
[0114] The biological activity of TNF in the blood plasma was evaluated by the cytolitic action on mice fibroblasts L-929. The indicator cells suspension (5×10 6 cells/ml) was introduced in portions of 100 μl into flat-bottom 96-alveola-culture panel and cultivated for 24 hours at 37° C. in 5% CO 2 atmosphere. Then cultural medium was removed from the alveola and 100 μl of test sample and 100 μl of cultural medium containing actinomycin D (final concentration 1n/ml) were added to a mono-layer of cells. Cells cultivated without test samples served as a control. After 24 hours of incubation the cultural medium was removed, the cells were stained with 0.2% solution of crystal-violet during 10 min at a room temperature, washed out for three times with water and dried at 37° C.
[0115] The results were evaluated using Multi-scan DYNARECH (Swiss) at a wavelength of 550 nm.
[0116] The TNF activity was evaluated beyond the cytotoxicity index (CI), which was calculated using the following formula: CI=(K−D)/K×100%, Where K is the optical density in control alveola and D is the optical density in test alveola
[0117] TNF recombinant preparation “Rifnamen” made by “VECTOR” (Ukraine) was used for TNF testing.
[0118] Functional activity of phagocytosis system was investigated in the nitro blue tetrazolium recovery (NBT test) by cytochemical methods.
8 . Tremella Extracts and Plant Resistance to Plant Viruses
[0119] Virus: Tobacco mosaic virus (TMV), strain U1;
[0120] Plants: Tobacco ( Nicotiana tabacum L.) variety Immune 580 and Datura stramonium L., cultivated in a hothouse under conditions of natural lighting, humidity, and temperature. Plants at a stage of 4-6 leaves were used in the experiment.
[0121] Polysaccharides, extracted from culture liquid of Tremella mesenterica were employed in this study using the method of Kovalenko with some modifications. To isolate acid glucuronoxylomannan (GXM) from neutral polysaccharides, we applied its sedimentation from a water solution with acetone (1:1) in the presence of 0.05 M CaCl 2 . Gas chromatography was carried out on Sephadex G-50 (2.5×80 cm) in pyridinium-acetate buffer, pH 4.5 (4 mL pyridine and 10 mL AcOH in 1 L water) and the eluate was monitored by refractive index detector.
[0122] In in vitro experiments the water solutions of the total preparation, neutral polysaccharide preparations, and pure GXM at concentrations of 10, 100, 500, and 1000 μg/mL were added to a suspension of TMV (10 μg/mL). After incubation over the 30 min the left halves of datura 's leaves were inoculated with this mixture. The right halves of leaves were inoculated with TMV at the same concentration without polysaccharides. The degree of inhibition of viral infection, or VIR, was counted (in percentage) according to the number of local lesions on the experimental and control halves of the leaves by the following formula: I=((K−D)/K) 100%, where I—is a degree of virus inhibition or level of AVR, %; K—is the number (size) of local lesions in the control; D—is the number (size) of local lesions in the experiment.
[0123] Investigations of induced properties of GXM were carried out on the tobacco and datura plants. For this purpose, the hydrogen solutions of polysaccharides at concentrations of 1000-2500 μg/mL were injected into the intercellular space of the left halves of the leaves with a 1 mL (insulin) syringe. The two halves of leaves were inoculated by TMV (1-5 μg/mL). The degree of AVR was taken into account by the formula mentioned above.
[0124] When studying the GXM-induced mechanism of plant resistance, we used actinomycin D (AMD) inhibiting the DNA-dependent synthesis of mRNA by blocking RNA-polymerases. Solutions of AMD at the concentrations of 10 and 20 μg/mL and rhamnolipide (RL)−1 mg/mL, which were subepidermally introduced simultaneously or via definite periods of time after the GXM. Differences in the number and size of local lesions were assessed by the criterion of Student (t) test; the resulting α-value is displayed in the tables by the following symbols: +++p≦0.01%; ++0.1≦p≦1%; +1%≦p≦5%; 0p>5%.
Example 1
Characteristics of the variety Coprinus comatus CBS 123401
[0125] Vegetative mycelium in pure culture. Mycelial colony white, cottony, often develops “tufts” (hyphal aggregates) with maturity. Asymmetrically shaped, usually forms mycelial mats along the outer edge. Clamp connections, anastomoses, and hair-like crystals are often present on hypha.
[0126] Pileus 3-15 cm; oval to rounded-cylindrical when young, expanding to bell-shaped with a lifting margin; in age turning to black “ink”; dry; whitish with a brownish center; with large, shaggy scales; margin lined at maturity. Lamellae free from the stem; white, becoming pinkish, then black; turning to black “ink”; very crowded. Stipe 5-20 cm long; 1-2 cm thick; frequently tapering to apex; smooth; white; easily separable from cap; hollow, with a string-like strand of fibers hanging inside. Context white throughout, soft. Spore print black. Basidiospores 9-13×7-9 μm; elliptical; smooth; with a central to slightly eccentric pore. Basidia 4-spored, 28-43×10-13 μm, surrounded by 5-8 pseudoparaphyses. Pleurocystidia absent. Cheilocystidia variously shaped; up to 60×40 μm. Pileipellis made of cylindric elements 7-30μ wide. Only pseudoclamps presents.
[0127] Habitat. It grows in groups in places which are often unexpected, such as green areas in towns. It occurs widely in grasslands and meadows.
Example 2
Evaluation of Coprinus comatus Antioxidant Activity
[0128] 2.1 Yield of Biomass and Extracts from Dried Submerged Cultivated Mushroom Mycelia
[0129] Nutrition medium selected for the submerged cultivation of higher Basidiomycetous mushrooms during the screening program ensured growth of all selected species. However, the yield of mycelial biomass after 8-11 days of Coprinus comatus CBS 123401 mushroom cultivation in identical culture conditions was 6.8 g/l (Table 1).
[0130] The extraction of soluble compounds from dried and milled mushroom mycelia was performed with culture liquid (instead of water) and ethanol. Significant differences in yield among the extracts received from different strains were revealed. Moreover, the yield of extracts received from mushroom biomasses significantly depended on the solvent used. The extraction with culture liquid of Coprinus comatus CBS 123401 biomass yielded 23.2% of extract.
[0131] Extraction with ethanol was less effective and a weak solubilizer used on the studied strain yielded only 8.5%.
[0000] 2.2 Antioxidant Activity of Water (Culture Liquid) and Ethanol Extracts from Submerged Cultivated Coprinus comatus CBS 123401 Mushroom Mycelium
[0132] Data presented in Table 2 show the antioxidant activity (AOA) of water (Culture Liquid) extracts received from Coprinus comatus CBS 123401. Very high AOA was revealed when C. comatus CBS 123401 water extracts in concentration of 2 mg/mL were used. Slightly lower AOA was observed in water extracts from Coprinus comatus CBS 123401 mycelial biomas. The inhibition values of all these extracts practically did not change with an increase of their concentration in the reagent mixture.
[0133] The AOA of ethanol extracts from mushroom biomass not only depended largely on the higher Basidiomycetes species, but also on the variation of extract concentration in the reagent mixture. When the concentration of ethanol extract increased from 2 mg/ml to 4-8 mg/ml, the AOA of extracts from Coprinus comatus CBS 123401 increased from 74.4 to 86.4% (Table 3).
[0000]
TABLE 2
Antioxidant activity (%) of water extracts from dried
submerged mushroom mycelia
Extract
concentration
(mg/mL)
Species
2.0
4.0
8.0
Coprinus comatus CBS 123401
83.8
88.4
91.6
Standard BHA (mg/mL in methanol)
98.2
—
—
BHA—Butylated hydroxyanisole
[0000] TABLE 3 Antioxidant activity (%) of ethanol extracts from dried mushroom mycelia Extract concentration (mg/ml) Species 2.0 4.0 8.0 Coprinus comatus CBS 123401 74.4 81.3 86.4 Standard BHA (mg/ml in methanol) 98.2 — — BHA—butylated hydroxyanisole
2.3 Free-Radical Scavenging Activity of Water (Culture Liquid) and Ethanol Extracts from Submerged Cultivated Mushroom Mycelia
[0134] Free-radical scavenging is one of the known mechanisms by which antioxidants inhibit lipid oxidation. The method of scavenging 1,1-diphenyl picrilhidrazyl (DPPH) free radicals was used to evaluate the antioxidant activity. DPPH, a stable free radical generating substance with a characteristic absorption at 520 nm, was used to study the radical-scavenging effects of extracts. The decrease in absorbance is taken as a measure of the extent of radical-scavenging.
[0135] The highest free radical-scavenging activities of the water and ethanol extracts were measured at sample concentrations of 0.5 mg/ml (27.0% and 22.0%, respectively), but the values were much lower than that of the standard (92.0%) (Tables 4 and 5).
[0136] The free radical-scavenging capacities of ethanol extracts of Coprinus comatus CBS 123401 decreased from 22 to 1, with a sample concentration increase from 0.5 to 9 mg/ml %, respectively. (Table 5).
[0000]
TABLE 4
Scavenging ability (% of inhibition) and EC50 values of water
(culture liquid) extracts from the submerged mushroom mycelium
of Coprinus comatus CBS 123401
Water extract (mg/ml)
EC 50
Species
0.5
1.5
3.0
9.0
(mg/ml)
Coprinus comatus
27 ± 2.7
22 ± 4.2
15 ± 2.1
0
1.7 ± 0.3
123401
BHA (1 mg/ml)
92 ± 2.1
BHA—Butylated hydroxyanisole;
EC 50 —Half maximal effective concentration
[0137] The values of effective concentrations for DPPH scavenging effects given in Tables 5 and 6 show evidence that the EC 50 of both water and ethanol extracts appeared to be near 1 mg/mL.
[0000]
TABLE 5
Scavenging ability (% of inhibition) and EC 50 values of ethanol
extracts from the submerged mushroom mycelium of
Coprinus comatus CBS 123401
Ethanol extract (mg/ml)
EC 50
Species
0.5
1.5
3.0
9.0
(mg/ml)
C. comatus
22 ± 2.1
17 ± 1.7
5 ± 1.4
3 ± 0.4
1.3 ± 0.4
CBS 123401
BHA
92 ± 2.1
(1 mg/ml)
BHA—Butylated hydroxyanisole;
EC 50 —Half maximal effective concentration
Example 3
Study on Biological Activity of Water (Culture Liquid) and Ethyl Acetate Extracts from Submerged Cultivated Mycelium of Coprinus comatus CBS 123401
[0138] 3.1 pIκBα Levels after NF-κB Stimulation in MCF7 Cells by H 2 O 2
[0139] Numerous studies on medicinal mushrooms proved their exclusive potential not only as dietary supplements and immunoenhancers, but also as the source of modulators of various cellular responses. Despite the observed success of most of the chemotherapeutic regimes, cellular adaptations have enabled tumor cells to become resistant to many chemotherapeutic drugs. One of these cellular chemo-resistance factors is the nuclear factor kappa B (NF-κB), which was shown to promote tumor proliferation. The activity of NF-κB is tightly regulated by interaction with IκB proteins. As with the NF-κB proteins, there are several IκB proteins that have different affinities for individual NF-κB complexes, but are regulated slightly differently and expressed in a tissue-specific manner.
[0140] Extracellular stimuli lead to the activation of IκB kinase (IKK) that phosphorylates IκB on two conserved serines (Ser32 and Ser36 in IkBα). This phosphorylation marks IκB for proteasomal degradation, resulting in the nuclear translocation and activation of NF-κB. This is considered the classic pathway of NF-κB activation. Several alternative pathways of NF-κB activation have been described. In the current study of the activation of NF-κB, hydrogen peroxide was used, which is a well known NF-κB activator and a strong oxidative reagent. The preliminary data showed that a 10-min treatment with 100 μM of H 2 O 2 caused the highest level of pIkBα, and treatment with 10 μM of curcumin, which is a known antioxidant and anticancer reagent, significantly inhibited pIκBα level. MCF7 cells were stimulated with 50 and 100 μM H 2 O 2 for increasing time periods. For 20 and 40 min 50 μM of H 2 O 2 stimulation showed high level of phκBα compared to the control, DMSO (dimethyl sulfoxide)-treated cells, where no H 2 O 2 was added. The highest level of pIκBα was shown by 100 μM H 2 O 2 -treated cells at 10-min stimulation (not shown. Therefore, the best conditions for checking the potential effects of extracts on pIkBα levels were established at 10 min H 2 O 2 -stimulation along with selected fungal extracts.
[0141] (MCF7 cells were stimulated with 50 and 100 μM of H 2 O 2 for increasing time periods. Stimulation with 100 μM of H 2 O 2 at 10 min intervals showed the highest level of pIκBα compared to the control, using DMSO-treated cells where no H 2 O 2 was added. Data represent results of one of two similar experiments).
[0000] 3.2 Effect of Coprinus comatus CBS 123401 Crude Extracts on Cell Viability
[0142] In the current experiments, Coprinus comatus CBS 123401 was investigated. C. comatus cultural liquid (water) (E1) and ethyl acetate (E2) crude extracts were tested for their ability to affect cell viability of MCF7 cell line and IC 50 s were calculated. Extract E2 appeared to be the most potent with IC 50 of 32 μg/ml, followed by E1 with IC 50 of 76 μg/ml (Table 6). These results indicate that the active moieties of C. comatus CBS 123401 extract were concentrated in extract E2. Extract E1 did not affect cell viability in a significant manner, however, this assay revealed that extract E2 demonstrated higher growth inhibition activity than E1, arguing that E2 might possess some bioactive compounds with possible anticancer activity.
[0000]
TABLE 6
Cell cytotoxicity of Coprinus comatus CBS 123401 extracts
Coprinus comatus
CBS 123401 crude
IC 50 ± SD μg/ml
E1 (Water extract)
76 ± 1.41
E2 (Ethyl acetate extract)
32 ± 0.71
[0143] Cells were treated with increasing concentrations of Coprinus comatus extracts. After 48 h, cells were collected, stained with 0.4% trypan blue solution (1:1), and counted using a hemacytometer. Percent inhibition of cells' viability was calculated against the DMSO-treated control. Values (μg/ml) are represented as the mean IC 50 s of a duplicated experiment±standard deviation.
[0000] 3.3 Coprinus comatus CBS 123401 Crude Extracts Effect on the IκBα Phosphorylation
[0144] The NF-κB pathway has emerged as one of the most promising targets in cancer drug discovery. Coprinus comatus CBS 123401 extracts were found to modulate the NF-κB activation pathway. In order to establish the effects of the two extracts of C. comatus , E1 and E2, on pIkBα level, MCF7 cells were stimulated for 10 min with 100 μM of H 2 O 2 as described above. The preliminary data showed that a 10-min treatment with 100 μM H 2 O 2 caused the highest level of pIκBα (not shown). C. comatus extracts were tested for their ability to affect κBα phosphorylation in 10-min cell stimulation with H 2 O 2 . Results showed that both extracts significantly affected IκBαphosphorylation in a dose-dependent manner. The organic extract E2 appeared to be the most active inhibitor of IκBα phosphorylation in both concentrations (100 and 200 μg/mL) used. As presented in FIG. 2 , extract E2 almost completely inhibited IκBα phosphorylation at the concentration 200 μg/mL and caused partial inhibition in the phospho-IκBα level at a concentration of 100 μg/mL. The extracts' effect is comparable to the effect of curcumin, which also demonstrated a high phospho-IkBα inhibitory effect ( FIG. 2 ).
[0145] In contrast with these results, the extract E1 at concentrations of 100 and 200 μg/ml only partially inhibited the phosphorylation of IkBα( FIG. 3 ).
[0146] The fact that E2 extract was a much more potent inhibitor than E1 extract indicates that lipid soluble substances are quite potent inhibitors of the NF-κB pathway.
[0000] 3.4 The Effect of Coprinus comatus E1 and E2 Extracts on the IKK Activity
[0147] The major activator of NF-κB is the IkB kinase complex (IKK). This complex includes two catalytic subunits, IKK-α and IKK-β, and a regulatory subunit, IKK-c (also known as NEMO). The NF-κB pathway is triggered by bacterial and viral infections as well as pro-inflammatory cytokines and chemokines (e.g., tumor necrosis factor a (TNF-a), lipopolysaccharide (LPS), interleukins (IL-1, IL-6), etc.), all of which activate the IKK complex phosphorylation by IKK β of two specific serines near the N terminus of IκBα, which targets IκBα for ubiquitination and degradation by the proteasome. Almost all signals that lead to the activation of NF-κB converge on the activation of a high-molecular-weight complex that contains a serine-specific IKK. Activation of the IKK complex leads to phosphorylation by IKK β of two specific serines near the N terminus of IκBα, which targets IκBα for ubiquitination and degradation by the proteasome.
[0148] On the basis of the abovementioned results it was assumed that the NF-κB inhibitory effects of the active extracts are due to modulation of the NF-κB pathway upstream of IkBαphosphorylation. IKK complex phosphorylates IκBα at serines 32 and 36, which leads to ubiquitination and degradation of IκBα by the 26S proteasomes. In order to establish whether E1 and E2 affect IKK activity, an ELISA-based IKK activity assay was applied. The effect of E1 and E2 extracts on IKK activity is presented in FIG. 4 . Received data showed that only the E2 extract inhibited the activity of IKK complex as compared to the control of the untreated sample. Moreover, E2 exhibited a strong effect, comparable to the effect of the positive controls used, 5-(p-Fluorophenyl)-2-ureido]thiophene-3 carboxamide (Fuct), and to MO04- Marasmius oreades crude ethyl acetate extract.
Example 4
Content and Chemical Composition of Submerged Cultivated Mycelium of Coprinus comatus CBS 123401
[0149] The chemical composition of submerged cultivated mycelium of Coprinus comatus was established by conventional methods well known in the art and is disclosed in Table 7 and Table 8.
4.1 Chemical Content.
[0150]
[0000]
TABLE 7
Content and chemical composition of Coprinus comatus CBS 123401
Test
Units
Result
Comment
Energy
Kcal/100 gr
349
1
Protein
%
37
2
Water content
%
13.5
—
Ash
%
5.5
—
Fats and Oils
%
5
—
Carbohydrates
%
39
3
Profile of the fatty acid GC-FID
Pentadecanoic acid (C15:0)
%
1.4
palmitic (C16:0)
%
11.8
palmitoleic acid (C16:1)
%
5.4
heptadecanoic acid (C17.0)
%
0.8
stearic (C18:0)
%
3.3
Oleic (C18:1n9c)
%
6.1
Linoleic (C18:2n6t)
%
0.4
Linoleic (C18:2n6c)
%
66.6
Linolenic (C18:3n3)
%
1.1
Linolenic acid (C18:3n6-γ)
%
1.1
Arachidic acid (C20:0)
%
0.2
Heneicosanoic acid (C21:0)
%
0.3
Behenic acid (C22:0)
%
0.5
Lignoceric acid (24:00)
%
0.6
Full metal screening at ICP
Al—Aluminium
mg/Kg
<10
As—Arsenic
mg/Kg
0.2
B—Boron
mg/Kg
4
Ba—Barium
mg/Kg
0.4
Be—Beryllium
mg/Kg
<0.5
Ca—Calcium
mg/Kg
4047
Cd—Cadmium
mg/Kg
<0.1
Co—Cobalt
mg/Kg
0.2
Cr—Chromium
mg/Kg
0.3
Cu—Copper
mg/Kg
8
Fe—Iron
mg/Kg
41
Hg—Mercury
mg/Kg
<0.5
K—Potassium
mg/Kg
14525
Li—Lithium
mg/Kg
<0.5
Mg—Magnesium
mg/Kg
2124
Mn—Manganese
mg/Kg
2
Mo—Molybdenum
mg/Kg
<0.5
Na—Sodium
mg/Kg
1136
Ni—Nickel
mg/Kg
1
P—Phosphorus
mg/Kg
11359
Pb—Lead
mg/Kg
0.3
S—Sulfur
mg/Kg
3596
Se—Selenium
mg/Kg
0.6
Sn—Tin
mg/Kg
0.8
Sr—Strontium
mg/Kg
2
Ti—Titanium
mg/Kg
1
V—Vanadium
mg/Kg
0.3
Zn—Zinc
mg/Kg
74
— = No comments
1. Energy—calculated from the content of protein, fats and carbohydrates at the sample.
2. Protein—protein calculation factor 6.25.
3. Carbohydrates—the result was calculated according to content of: water, ash, fat and protein at the sample.
4. Test results are given at relative percentage from the oil.
5. Metal screening—result with ‘<’—trails are not found at the mentioned sensitivity limit.
[0151] Mycelia of Coprinus comatus CBS 123401 contained 17 free amino acids, 10 of which are essential amino acids (with asterics): γ-aminobutyric acid*, alanine, arginine, aspartic acid, glutaminic acid, glycine, histidine*, isoleicine*, leucine*, lysine*, methionine*, phenylalanine*, serine, threonine*, tryptophan*, tyrosine, and valine*.
[0000] TABLE 8 Vitamin content of Coprinus comatus CBS 123401 Test Units Result Comment Vitamin B1 (Thiamine) mg/100 gr 7.5 Vitamin B2 (Riboflavin) mg/100 gr 0.45 Vitamin A (Retinol) μg/100 gr <50 Vitamin C (Ascorbic acid) mg/100 gr 6.15 Vitamin E (α-Tocopherol) mg/100 gr <1 Vitamin B 3 (Niacin + N.amid) mg/100 gr <1
4.2 Analysis of the Polysaccharide Composition of Coprinus comatus CBS 123401 Submerged Cultivated Biomass.
[0152] Washed cells were extracted by hot water in an autoclave at 120° C. for 1 h; the precipitate was removed by centrifugation. A small amount of solution was dried and analyzed by NMR. The spectra ( FIG. 5 ) showed intense sharp signals of low-molecular mass components and typical protein-polysaccharide background. 2D spectra of this product were recorded and low-molecular mass components were identified as trehalose (α-Glc-1-1-α-Glc, a characteristic component of mushrooms such as shiitake ( Lentinus edodes ), maitake ( Grifola fondosa ), nameko ( Pholiota nameko ), and Judas's ear ( Auricularia auricula - judae ), which can contain 1% to 17% percent of trehalose in dry weight form), and mannitol, in the molar ratio ˜1:1. Mannitol content was estimated by GC analysis: 1% w/w of inositol (internal standard) was added to the fresh cells, and the mixture was acetylated by acetic anhydride-pyridine at 100° C. for 1 h. GC analysis showed that the mannitol content of the cells was 3% by weight, consequently trehalose content is 6% (it has molecular mass twice that of the mannitol).
[0153] The residue after water extraction was treated with 5% NaOH (100° C., 3 h); precipitate was removed by centrifugation; solution was dialyzed and dried; the yield was 400 mg; protein content was 30% and carbohydrate content was 55%.
[0154] Monosaccharide analysis of the whole cells, extracts, and residues after extraction was performed; results are shown in the Table 9 and FIG. 6 . Cells and solid residues were dissolved in concentrated HCl at 40° C. for 1 h and then diluted with water to a final acid concentration of 2M. Other samples were directly dissolved in 2M HCl. Hydrolysis was carried for 2 h at 100° C., products were dried, sugars were converted into alditol acetates (NaBH 4 reduction and acetylation with Ac 2 O), and analyzed by GC. Glucose content of the solid residues after extraction increases because insoluble β-glucan remains in the residue, and soluble components are progressively removed by extraction.
[0000]
TABLE 9
Monosaccharide composition of Coprinus comatus and extracts
Man
Glc
Gal
GlcN
EtOH washed cells
6
48
2
10
Water extract
8
26
3
0
NaOH extract
2
60
2
0
Cells without hydrolysis
3
Cells after water extraction
2
40
2
25
Cells after water and NaOH
1
30
0
50
Monosaccharide composition of the cells and extracts (% w/w), measured by GC relative to internal inositol.
Samples were dissolved in concentrated HCl (37°, 1 h), diluted with 5 vol of water to 2M HCl, heated 2 h at 100°, reduced and acetylated.
“Cells without hydrolysis” were just acetylated to measure the content of free mannitol
[0155] Removal of low-molecular mass components from the water extract by dialysis left a product, containing 25% carbohydrates and 40% proteins as determined by colorimetric tests (phenol-sulfuric acid for the polysaccharides and Lowry for proteins). Polysaccharides were identified as starch, β-glucan, and fucogalactan on the basis of NMR spectra. Starch amylose (2% w/w from cells) has been isolated in pure form by CaCl 2 precipitation. Galactan content was estimated as 3% from the monosaccharide analysis. Fucose content of the whole extract and cells was too low for quantification. The structure of the galactan was analyzed by NMR and methylation and is shown below:
[0000]
[0156] Polysaccharides from water and NaOH extracts were partially separated by size-exclusion chromatography on Sephadex G-50 ( FIG. 7 ). Starch was eluted first and was identified by 1 H NMR spectrum. Galactan also was eluted close to the void volume, which agreed with published data on its molecular mass, estimated as 10,000 Da. Void volume (excluded volume) for Sephadex G-50 is 10,000 Da for dextran. Galactan was eluted close to ovoid, but slightly retained (thus its molecular mass was not greater than excluded mass), so it had max mass of 10,000 Da. It also was presented in lower mass fractions.
[0157] Soluble β-glucan had wide distribution of molecular mass from 10,000 to <1000 with no visible dominant mass. As one can see from the chromatogram ( FIG. 7 ) β-glucan was elited as a very broad peak from vpid volume to the salts, spanning whole fractionation range of Sephafex G-50 (500-10,000 Da). It was not possible to prepare pure β-glucan; it contained some amount of starch, galactan, and protein. Anion-exchange chromatography improved spectra quality due to the removal of part of protein, but polysaccharides did not separate completely. Because of low-molecular mass of glucan, some amount of glucan was lost during dialysis and gel chromatography.
[0158] Methylation analysis of (3-glucan showed the presence of terminal, 3-, 4-, 6-, and 3,6-substituted glucose residues in the ratio of 2:1:0.3:3:1. The methylation analyses suggests that side chains are attached to every third glucose of the main chain and that the average length of the side chain is 3 sugars (t-Glc:6-Glc˜1:2, 3-Glc:3,6-Glc˜2:1). The presence of 4- and 4,6-substituted Glc may originate from starch. Peaks of 2- and 2,6-substituted Gal belonged to the galactan.
[0159] NMR analysis of the β-glucan fraction showed its similarity to Ganoderma glucan ( FIG. 8 and Table 10). The structure is shown below:
[0000]
[0000] wherein m is an integer between 1 and about 10 and n is an integer equal to about 3.
[0160] For the quantification of the starch and insoluble β-glucan content the Megazyme assay “Mushroom and beta-glucan” was used. Measurements were performed according to the manufacturer's instructions. Samples of cells, water-extracted cells, water and NaOH-extracted cells, water extract and NaOH extract were analyzed. The results are shown in Table 11. Megazyme assay “Mushroom and beta-glucan” is based on the measurement of total glucose, released by a combination of hydrolysis and enzymatic treatment and a separate measurement of the starch content. β-glucan content is calculated as the difference of the first two numbers. No direct measurement of β-glucan is used.
[0000]
TABLE 10
NMR data for the Coprinus comatus β-glucan (ppm; D2O, 25° C.).
H/
H/
H/
H/
H/
H/
Unit
Nucleus
C-1
C-2
C-3
C-4
C-5
C-6
Glc
H
4.76
3.31
3.51
3.40
3.46
3.72/3.91
C
104.2
74.7
77.1
71.1
77.4
62.3
−3-Glc
H
4.52
3.51
3.75
3.51
3.50
3.72/3.91
C
104.2
74.5
85.9
69.7
77.1
62.3
−3,6-Glc
H
4.52
3.51
3.75
3.57
3.62
3.86/4.20
C
104.2
74.5
85.9
69.6
76.4
70.4
[0000]
TABLE 11
Total glucan, α-glucan and β-glucan content of
Coprinus comatus samples
Glucan content % w/w
Total
α-
β-Glucan
EtOH washed cells
46.6
5.1
41.5
Water extract
28.2
15.1
13.1
NaOH extract
35.3
12.3
22.0
Cells after water extraction
42.0
8.0
34.0
Cells after water and NaOH
35
5
30
CONCLUSION
[0161] The results of this study show that Coprinus comatus produces β-glucan with β-1-3-glucose main chain with 1-6 linked side chains, similar to the soluble β-glucan extracted from Ganoderma lucidum mushrooms. C. comatus also produces fucogalactan, starch, trehalose and mannitol; all of these components were previously found in mushrooms. Soluble β-glucan has low-molecular mass and is easily extractable with hot water.
[0000] 4.3 Lectin content. Tested species Corpinus comatus CBS 123401 biomass possesses hemagglutinating activity (Table 12). A very high lectin hemagglutinating titer (18585) was revealed in biomass extracts from C. comatus . Specific hemagglutinating activity of C. comatus reached 62700 U mg −1 .
[0000]
TABLE 12
Corpinus comatus CBS 123401 biomass protein content,
hemagglutinating activity and sugars specificity
Total
HA
Specific HA
Specificity
MIC of
protein
titer,
activity
of
saccharides
Species
(mg)
(T-1)
(U mg−1)
saccharides
(mM)
Corpinus
71.5
18585
62700
Lac,
Lac (0.80)
comatus
GlcNAc,
Gal
MIC = minimal inhibition concentrations
HA = hemagglutinating activity
[0162] The data show that lactose followed by GalNAc and galactose are the most widespread inhibitors of hemagglutinating activity of tested mushroom lectin. Lactose was the most potent inhibitor of fungi. Lactose inhibited lectin activity of C. comatus at a concentration of 0.78 mM. At the same time, xylose, cellobiose, and dulcitol did not inhibit the lectin hemagglutinating activity of Coprinus comatus biomass
[0163] Obtained result showed that C. comatus have the capability to accumulate lectin in biomass and fruit bodies. Especially high hemagglutinating activity was revealed in C. comatus . The determination of sugar specificity toward mushroom lectins showed that lactose binding lectins are the most widespread among the tested strain.
Example 5
Characteristics of the Variety Tremella mesenterica CBS 123296
[0164] Vegetative mycelium in pure culture. Mycelial colony white, cottony, often develops “tufts” (hyphal aggregates) with maturity. Asymmetrically shaped usually forms mycelial mats along the outer edge. Clamp connections, anastomoses, and hair-like crystals are often present on hypha.
[0165] Basidiocarps often large and conspicuous, 2-10 cm wide and up to 5 cm high, mostly solitary, gelatinous, cerebriform when young and moist, later foliose with irregular clustered folds, consisting of several undulate-plicate lobes, yellow to yellowish-orange in fresh specimens, occasionally paler or entirely unpigmented and white when old, in wet or dark environments, yellowish-orange to darker when dry. Hymenial surface smooth, more or less shiny. Flesh gelatinous and soft. Hyphal system monomitic. Hyphae with abundant clamp connections, hyaline, thin- to thick-walled, mostly 1.5-3 μm wide, somewhat wider in the inner part of the basidiocarp, gelatinized. Haustorial cells globose to oblong, 3-6×2-4 μm wide, usually present except in young specimens, mostly abundant close to attachment point. Basidia of two types: 1) broadly ellipsoid to subglobose, 10-25×10-22 μm; 2) oval to clavate, 20-30(-35)×12-20 μm; longitudinally or obliquely septate, four spored, with sterigmata 100-150×2-3 μm wide, apically swollen up to 7 μm. Basidiospores broadly ellipsoid to oblong, (8-)10-16(-18)×(5-)7-10(-12) μm, smooth, hyaline, thin-walled, with an evident apiculus, negative in Melzer's reagent. Conidiophores densely branched, often abundant in the hymenium, particularly present in young specimens. Conidia subglobose to oval and, 3-5×2.5-3.5 μm, or ellipsoid to cylindrical 3-5×(1-)2 μm in diam., smooth, hyaline, often numerous. Hyphidia usually absent, sometimes present in early stages of development, thin to slightly thick-walled, up to 3.5(-4) μm wide. Vesicles variable in shape and size, ranging from globose to ellipsoid, mostly 20-30×5-10 μm, thick-walled. Spore print whitish or pale yellowish.
[0166] Habitat: on hardwood decayed branches, logs, and sticks.
[0167] Tremella mesenterica CBS 123296 has a special life cycle. In contrast to other higher Basidiomycetes mushrooms a single basidiospore germinates on a nutrient medium broth by hypha and by yeast-like budding cells. Monobasidiosporous culture is haploid, i.e. contains only one nucleus in each cell. When two compatible haploid cells, originating from different basidiospores, come into contact, a plasmogamy and caryogamy occurs and dycariotic mycelium develops. The dycariotic mycelium cannot grow in the form of budding cells, under any conditions of cultivation, so a yeast-like type of growth is genetically determined by a haploid status of mushroom culture. The haploid culture is more plastic, because on poor media or under conditions of exhaustion yeast-like cells can form haploid hypha. One-cell fungi cultures, like other microorganisms, are more acceptable for biotechnological processes, than mycelial ones. This is especially important for Basidiomycetes dycariotic cultures, which grow in the form of sterile mycelium, and a special procedure for preparing Basidiomycetes inoculum is needed, that includes dycariotic mycelium homogenization. The haploid yeast-like budding culture of the present invention, is the optimal form of growth not only from biotechnological considerations, but as defined by its physiological attribute of producing a larger amount of polysaccharide than mycelium form.
Example 6
Regulation of Growth and Biosynthetic Activity of Medicinal Jelly Mushroom Tremella mesenterica CBS 123296 Pure Culture
[0168] Fruit bodies of Tremella mesenterica were collected for basidiospore print development. Fruit bodies were associated with Peniophora sp. on a dead twig of Quercus sp. Haploid yeast-like cultures obtained from this specimen demonstrated fast growth on agar media, and 14 of them were used for primary screening in submerged culture conditions. A strain selected is deposited at Haifa University Culture Collection (HAI) under the name Tremella mesenterica CBS 123296.
[0169] Optimum pH value for selected strain biomass growth in submerged culture conditions was determined in a range from 5.5 to neutral meaning. The highest yield of biomass was obtained on liquid malt extract medium with pH 6.35.
[0170] Optimization of culture medium composition suitable for biomass accumulation have demonstrated that sucrose is as appropriate a source of carbon as is glucose.
[0171] A mixture of peptone and yeast extract is a good source of nitrogen, while ammonia salts investigated previously decreased pH of a media very rapidly. They contained also enough phosphorus for cell growth, as addition of phosphorus salts did not resulted in increased yield of biomass. Magnesium acetate is considered as more physiologically alkaline than MgSO 4 , and indeed prevented rapid acidifying of culture media.
[0172] Slightly modified culture medium was used further as a standard “inoculum media” of a following composition (g/l): sucrose—20.0; peptone—2.0; yeast extract—2.25; Mg acetate—1.0; KCl—1.0. pH of the medium after sterilization at 120° C. for 30 min. is close to 6.5.
[0173] The optimal composition of the “fermentation medium” was found to be as follows: Tremella mesenterica was cultivated in the medium prepared by mixing Part A consisting of (g/L) Sucrose, 50.0; Yeast extract 0.5; KCl, 1.0; Mg acetate.4H 2 O, 1.0 with Part B consisting of (g/L) NaH 2 PO 4 .H 2 O, 0.5 and Na 2 HPO 4 .7H 2 O, 1.0.
[0174] Part B was added to a flask with part A when solutions were cold to room temperature after sterilization.
[0175] Cultivation of T. mesenterica was continued for 72 h at which point TMP in culture liquid reached 27.0 g/l (Table 13). After precipitation, separation and drying 170 g of TMP preparation was received.
[0000]
TABLE 13
Culture parameters change during Tremella mesenterica CBS 123296
cultivation in fermentor.
Medium
Agitation,
Time, h
pH
DO, %
rpm
TMP, g/L
0
6.35
80.7
50
1.8
2
6.29
50.3
50
5
6.12
31.4
50
11
5.80
19.4
184
23
3.26
11.8
302
24
5.00
14.3
304
7.5
33
5.00
19.3
380
36
5.00
8.2
400
48
5.00
1.7
400
22.3
72
5.00
2.3
400
27.0
DO, Dissolved oxygen;
TMP, crude T. mesenterica preparation
Example 7
Content and Chemical Composition of Tremella mesenterica
[0176] 7.1 General composition. Tremella mesenterica CBS 123296 submerged culture crude product consists of cell biomass of a strain-producer and exocellular polysaccharide glucoronoxylomannan in equal proportion. The general composition in this case is presented in Table 14.
[0000]
TABLE 14
General composition of Tremella mesenterica CBS 123296
Test
%
Acidic α-(1-3) heteropolysaccharide
35.0
glucoronoxylomannan
Glycogen
6.0
Crude Dietary Fiber & B-glucan
31.8
Mineral Elements
6.2
Protein
20.0
Free amino acids
1.0
[0177] The chemical composition was determined at two different and independent facilities in Israel (Bactchem Co. and Aminolabs Co.), and is disclosed in Tables 15 to 17.
[0000]
TABLE 15
Chemical composition of submerged biomass Tremella
mesenterica CBS
Type of analysis
Units
Results
Oleic acid-C18:1
gr/100 g
1.6835
Linoleic acid-C18:2
gr/100 g
1.1618
Palmic acid-C16:0
gr/100 g
0.725
Palmitoleic acid-C16:1
gr/100 g
0.0185
Stearic acid-C18:0
gr/100 g
0.0888
Myristic acid
gr/100 g
0.015
Microelements
Ag—Silver (in ICP)
mg/100 g
<0.2
Al—Aluminum (in ICP)
mg/100 g
0.7
Ac—Arsenic (in ICP)
mg/100 g
<0.050
B—Boron (in ICP)
mg/100 g
<0.24
Ba—Barium (in ICP)
mg/100 g
0.3
Be—Beryllium (in ICP)
mg/100 g
<0.005
Ca—Calcium (in ICP)
mg/100 g
11766
Cd—Cadmium (in ICP)
mg/100 g
<0.050
Co—Cobalt (in ICP)
mg/100 g
<0.010
Cr—Chromium (in ICP)
mg/100 g
0.16
Cu—Copper (in ICP)
mg/100 g
0.26
Fe—Iron (in ICP)
mg/100 g
1.5
Hg—Mercury (in ICP)
mg/100 g
<0.025
[0000]
TABLE 16
Amino acid composition of submerged biomass of
Tremella mesenterica CBS 123296
Sample
Submerged
Analysis
Units
mycelium
Cysteic acid
%
0.02
2
Aspartic acid
%
0.12
—
Methionine sulfon
%
0.02
2
Threonine
%
0.08
—
Serine
%
0.08
—
Glutamic acid
%
0.14
—
Proline
%
0.07
—
Glycine
%
0.06
—
Alanine
%
0.08
—
Valine
%
0.04
—
Isoleucine
%
0.05
—
Leucine
%
0.11
—
Tyrosine
%
0.04
—
Phenylalanine
%
0.06
—
Lysine
%
0.04
—
Histidine
%
<0.01
—
Arginine
%
0.03
—
Total
%
1.03
—
Remarks:
— = No remarks
1. Tryptophan was not reported since it was destroyed completely during hydrolysis.
2. Cysteic acid & Methionine sulfon: Molecular weight represent Cysteine & Methionine, respectively.
[0178] 7.2 Crude dietary fiber includes hemicellulose, low molecular polysaccharides such as dextrin, and cell walls components such as β-(1-3)-glucans.
[0179] 7.3 Vitamins. In the biomass of Tremella mesenterica CBS 123296 were founf vitamins A (Retinol), C (Ascorbic acid), E (α-Tocopherol), and vitamins of group B.
[0000]
TABLE 17
Vitamin A and group B vitamins content in Tremella mesenterica
CBS 123296
Content, μg/g
Vitamins
dry weight
Vitamin A (Retinol)
1000
Vitamin B 1 (Thiamine)
1.28
Vitamin B 3 (Niacin)
400.0
Vitamin B 6 (Pyridoxine)
0.8
Vitamin B 7 (Biotin)
0.1
[0180] Among vitamins of group B, determined by the microbiological method, based on the estimation of growth characteristics of sensitive auxotroph microorganisms, T. mesenterica biomass is especially rich in niacin and is rich in vitamin A.
[0181] 7.4 Glucan and Glucuronoxylomannan in Tremella mesenterica (Cbs 123296)
[0182] Composition was determined by GC analysis (glucose, mannose and xylose content) of the whole Tremella mesenterica submerged biomass and of the fractions obtained after ultracentrifugation. Glucan completely precipitates at 120 000 g, glucuronoxylomannan (GXM) mostly remains in solution, although partly precipitates as well. It was found that GXM constitutes about 70% and Glucan about 30% of dry weight of the polysaccharide biomass.
[0183] Pure glucan without GXM was obtained by separation of the Tremella mesenterica treated by high power ultrasound. Ultrasound treated GXM is better soluble in water and does not precipitate in ultracentrifuge, thus pure β-glucan can be isolated after two re-precipitations. Separation of 1.2 g of Tremella mesenterica gave 400 mg of precipitate (glucan with ˜10% GXM) and 800 mg of soluble product (GXM).
[0184] In GC analysis GXM content was taken as (Man+Xyl)*1.3 (1.3 was used to compensate for GlcA and acetates). The structure of glucuronoxylomannan in the newly isolated Tremella mesenterica (CBS 123296) was found to be somewhat different from glucuronoxylomannan isolated from other Tremella mesenterica strains (not shown). Glucan was estimated from glucose content. To avoid reduction of glucuronolactone into Glc, hydrolysates were treated with 24% NH 3 prior to NaBH 4 reduction. Since glucan is not well soluble in the 3M TFA used for hydrolysis, other set of samples was treated with concentrated HCl (40° C., 1 h) before hydrolysis. This procedure leads to increased Glc recovery, but xylose partially degrades.
[0185] Methylation of the β-glucan showed that it has a linear structure with 3- and 4-substituted glucose as main components ( FIG. 9 and FIG. 10 ). Thus the glucan is a 3,4-β-glucan. The glucan is not well soluble in DMSO, thus it was methylated twice; still some part was not dissolved, which may influence the results. The glucan is not soluble in water.
Example 8
Interferonogenous and Immuno-Modulating Properties of Tremella mesenterica CBS 123296 Preparations
[0186] Mongrel mice weighting 18-20 g were used in the study. The mice were fed per os by submerged single cell biomass of Tremella mesenterica CBS 123296.
[0187] The mice were killed after 6, 24 and 48 hours after treatment with the preparations, then blood plasma was collected in which the interferon (IFN) and tumors necrosis factor (TNF) levels were determined, and macrophages of peritoneal exudate aimed for examination of the phagocytosis system functional activity response to the preparations.
[0188] 8.1 Plasma IFN Levels.
[0189] Interferogenic properties are presented in Table 18, and show that a single dose of biomass at 4 mg/animal given to mice per os induced synthesis of endogenous IFN in low titres (80 units/ml) after 24 hours. The IFN level in the blood serum of animals treated with the above dose of Tremella mesenterica biomass remained increased to 80 units/ml after 48 hours.
[0190] Tremella mesenterica biomass at a dose of 10 mg/animal appeared to be more active and caused generation of endogenous IFN in 80 units/ml titres 6 hours after administration. 24 hours after the preparation administration the IFN titres in the animal blood serum reached the maximum of 160-320 units/ml. Further (in 48 hours) the level of the serum IFN was reduced but still remained elevated (80 units/ml) in comparison with the control indices.
[0000]
TABLE 18
Determination of interferonogenous activity of Tremella mesenterica
CBS 123296 biomass preparations in vivo
IFN titre in units/ml
Time after the
preparation
Dose
injection, hours
Preparation
mg/animal
6
24
48
Physiological
—
20
<20
<20
solution (control)
Poly I:C
50
320
40
<20
T. mesenterica
4
20
80
80
biomass
10
80
160-320
80
[0191] According to the tumor necrosis factor (TNF) level in the blood plasma determined in the study, Tremella mesenterica biomass did not result in synthesis of this cytokine in vivo (not shown). At the same time these preparations might assist in reducing the endogenous body intoxication. This is evidenced by the TNF detected in the blood plasma of control mice (at introduction of physiological solution). The use of the preparation results in reduced amount of TNF in blood plasma of control animals.
[0192] 8.2 Response of the functional activity of macrophages of peritoneal exudate to Tremella mesenterica biomass. Functional activity of macrophages of peritoneal exudate was evaluated in Nitro Blue Tetrazolium (NBT)-test—the reaction of non-substrate reduction of nitro blue tetrazolium. The NBT test is commonly used for investigation of functional activity of macrophages, since the impaired NBT reduction ability of macrophages is concurrent with the pathology of their oxygen-dependent biocide properties. The activity of macrophages in NBT-test was examined without additional cells stimulation in vitro (spontaneous test) and with their stimulation in vitro with St. aureas cells (stimulated test). The stimulated NBT-test is regarded as a cytochemical criterion of the readiness to complete phagocytosis. The difference between the spontaneous and stimulated NBT-tests indices is regarded as cells functional reserve (FR), which reflects the effector potential of phagocytic system which fits well into the concepts about the general immunity reserves.
[0193] A single dose of Tremella mesenterica biomass at 4 and 10 mg/animal given per os was found to modify the oxygen-dependent biocide activity indices of macrophages of peritoneal exudate in spontaneous and stimulated NBT—tests (Table 19). It should be mentioned that the phagocyte activity response to Tremellastin was dependent on the dose and observation time. For example in 6 hours after a 4 mg/animal dose of Tremella mesenterica biomass was given, a slight drop of oxygen-dependent biocide activity and FR of macrophages occurred both in spontaneous and stimulated NBT-tests. Data presented in Table 19 show that after 24 and 48 hours the indices of the spontaneous NBT test increased reaching the control indices value in response to Tremella mesenterica biomass at 4 mg/animal. However, in comparison with the control a drastic increase of oxygen-dependent biocide activity of macrophage activity occurred in stimulated NBT-test during the given observation period (in 24 and 48 hours), which resulted in significant increase of their FR.
[0000]
TABLE 19
Oxygen-dependent bactericidal activity of macrophages in vivo
response to Tremella mesenterica CBS 123296 biomass preparation
Time
NVT-test
after
indices (%)
Dose
injection,
Sponta-
Stimu-
Functional
Preparation
(mg/animal)
hours
neous
lated
reserve
Control
—
—
55.2
64.6
9.4
T. mesenterica
4
6
44.5
47.5
3.0
biomass
24
48.5
74.0
25.5
48
56.0
85.0
29.0
T. mesenterica
10
6
64.5
83.0
18.5
biomass
24
56.6
75.8
19.8
48
56.0
94.0
38
[0194] In response to a single dose of 10 mg/animal of Tremella mesenterica biomass a slight increase of the indices of spontaneous NBT-test was observed after 6 hours, however after 24 and 48 hours the values reduced to the control index level. At the same time significant increase of macrophages activity was observed in stimulated NBT-test during the entire observation period—in 6, 24 and 48 hours. Increased stimulated NBT-test indices for mice macrophages treated with 10 mg/animal of Tremella mesenterica biomass resulted in drastic increase of FR cells. As follows from Table 19, FR increase occurred after 6 hours, and in 48 hours the maximum was attained.
[0195] As can be seen from our studies, Tremella mesenterica biomass had a minor influence on the indices of spontaneous NBT-test, however it caused significant increase of macrophages activity in stimulated NBT-test, in this way increasing the reserve potentialities of the phagocyte system.
[0196] As can be seen from the results of our investigation the oxygen-dependent bactericidal activity of macrophages in spontaneous NBT-test after 6 hours remained unchanged in comparison with the control. At the same time the stimulated NBT-test indices increased after 6 hours, which resulted in a significant increase of the cells FR. After 24 hours, the spontaneous NBT-test indices remained unchanged relative to the control, the indices of the stimulated test tended to increase and the FR of the cells remained unchanged too.
[0197] 8.3 Summary. According to the investigation results analysis, a single dose of 4 and 10 mg/animal of Tremella mesenterica biomass preparation results in minor interferonogenous activity, inducing generation of “late” endogenous interferon. Tremella mesenterica biomass preparation appeared to be a more active interferonogen, moreover it was most efficient when concentrated to 10 mg/animal. In response to 10 mg/animal of Tremella mesenterica biomass preparation the peak value (160-320 units/ml) of interferon titres in blood serum was reached in 24 hours, which then decreased still remaining high during the entire period of observation. Tremella mesenterica biomass would be expected to prime, initiating generation of small amounts of interferon in the animals body, namely to intensify the interferon synthesis when injected together with other interferonogens.
[0198] Intensified functional activity of peritoneal exudate macrophages in the NBT-test in response to Tremella mesenterica biomass was observed. Tremella mesenterica biomass concentrated to 10 mg/animal appeared to be the most efficient activator of oxygen-dependent biocide activity of macrophages. The preparation caused an increase of the stimulated NBT-test indices (at unchanged indices of the spontaneous NT-test), which resulted in drastic increase of the functional reserve of the phagocyte system. It should be mentioned that the increase of the reserve potentialities of the phagocyte system is important to prevent the development of opportunistic bacterial or virus induced infections. It is also likely to prevent additional pathogenic-induced contamination of the body. Higher bactericidal activity of macrophages as well as higher functional reserve (with the difference between the spontaneous and stimulated NBT-test indices) accounted for the Tremella mesenterica biomass preparation correlated with interferon generation in the body. In this connection the activation of oxygen dependent macrophages biocide activity is associated with the induction of endogenous IFN by the Tremella mesenterica biomass (and possibly other cytokines, which needs to be further examined) since phagocytes are the main target of the IFN action in the body. Moreover, it is not improbable that phagocytes activated by the preparation are capable to take part in the generation of endogenous IFN by autocrine and paracrine activation technique.
Example 9
The Effect of Tremella mesenterica Cbs 123296 Extract and Glucuronoxylomannan on Plant Resistance to Phytoviruses
[0199] When chemical properties of polysaccharides isolated from the culture liquid and fruit bodies of Basidiomycetes were studied, we revealed neutral and acid polysaccharides. In particular, the acid polysaccharide of glucuronoxylomannan (GXM) produced by Tremella mesenterica consists of linear backbone of α-(1→3)-linked mannan, glycolized by β-(1→2)(1→4)-linked oligosaccharides of xylose and glucuronic acid, which gives the polyanion properties. Based on known data, it is possible to assume that neutral and acid glycans have different characteristics of antiphytoviral activity.
[0200] Indeed, the investigated polysaccharides differently inhibited the development of local lesions induced by TMV on Datura plants (Table 20).
[0201] Neutral polysaccharides proved to be the most active. The depression of the local lesions formation was up to 80 and 99.4% (in concentration of 100-1000 μg/mL). GXM was considerably less active, and, in this case, the total preparation occupied an intermediate position revealing evidence that the total preparation activity relative to infectivity of TMV is induced to a greater extent by neutral polysaccharides. The latter confirms the data from literature in which neutral polysaccharides relative to viral infectivity in supersensitive plants are more active than their sulfate derivatives, which mainly induce virus resistance of plants de novo. Based on the obtained results, it was important to investigate if GXM, which similar to sulfated mannan, can induce genetically dependent resistance of plants to viruses. It was found that GXM at a concentration of 1000-2500 μg/mL may induce resistance of the tobacco and datura plants to TMV (Table 21). In this case, AVR appeared to be higher in the tobacco plants than in datura plants. In other words, the activation of AVR by this polysaccharide depends on the genotype of the supersensitive host plant, and, consequently, on the activity of the proper gene of resistance.
[0000]
TABLE 20
Influence of Tremella mesenterica CBS 123296 GXM and neutral
polysaccharides on infectivity of TMV in Datura stramonium plants
Number of local
Concentration
lesions per leaf
Polysaccharides
μg/mL
Experiment
Control
Inhibition, %
Total
1000
0.5
11.9
96**
500
2.3
5.6
57*
Neutral
1000
0.2
31.9
99.4*
100
0.8
4.1
80*
GXM
1000
1.3
9.0
860
100
4.5
5.2
16*
10
26.5
17.4
−510
Note:
P0 > 5%;
*1% < P ≦ 5%;
**0.1% < P ≦ 1%;
*** P ≦ 0.1%
[0202] The investigation of the resistance development has shown that GXM at the concentration of 1000 and 2500 μg/mL induces the development of AVR relative to TMV in the tobacco plants already in the first day after inoculation with the inducer ( FIGS. 11 and 12 ). For the concentration of GXM, which equaled 1000 μg/mL under the continued polysaccharide presence in plant tissues, the level of resistance gradually decreases: to 30%—in the 5th and to 20%—in the 7th days ( FIG. 11 ). For the concentration of GXM, which equalled 2500 μg/mL, such a tendency is not observed ( FIG. 12 ). On the contrary, this fact may provide evidence not only on the concentration dependence of polysaccharide induction of AVR at the gene level but also about the different ability of plants to adapt to lower and higher concentrations of GXM.
[0000]
TABLE 21
Influence of glucuronoxylomannan on induction of resistance
against TMV-infection in Nicotiana tabacum and Datura
stramonium plants
Number of local
Concentration
lesions per leaf
Level of induced
μg/mL
Experiment
Control
resistance, %
Nicotiana tabacum , variety Immune 580
100
98.1
100.0
20
500
102.7
104.7
20
1000
128.5
155.0
17*
2000
63.4
133.1
52**
Datura stramonium
100
71.2
79.8
110
500
90.0
99.3
90
1000
119.9
139.1
14*
2000
119.6
181.1
33**
Note:
see Table 20.
[0203] On measuring the sizes of TMV local lesions on the experimental and control halves of leaves, it was revealed that at the concentration of 2500 μg/mL GXM intensifies the growth of viral lesions ( FIG. 13 ). At this concentration of GXM the reliable stimulation of the growth of necroses is observed only 7 days after inoculation with an inducer into the plant tissue, although such a tendency is observed in other periods of polysaccharide employment. On the halves of leaves treated with GXM at the concentration of 1000 μg/mL, reliable differences were not observed in the size of local lesions between the experiment and control.
[0204] It is known that similar influence on the growth of local necroses is produced by yeast RNA. This phenomenon may be explained by the activation in plants of the supersensitive mechanism of resistance under the influence of an inducer.
[0205] It was established in experiments with actinomycin D (AMD) that this antibiotic inhibits the development of GXM-induced virus resistance of plants ( FIG. 14 ). AMD, irrespective of the method of its application (simultaneously or 2 days after introduction of GXM), inhibited the development of AVR induced with polyanion, either partly (20 μg/mL) or completely (10 μg/mL). Incomplete inhibition of AVR by actinomycin D at the concentration of 20 μg/mL may be caused by the antibiotic toxicity relative to plant tissues. The latter is confirmed by a decrease in the number of necroses in the control, where AMD was injected into leaves in the absence of GXM.
[0206] On the whole, the results obtained lead to the conclusion that AVR inoculated into supersensitive plants by GXM depends on the synthesis of new RNA on the matrices of cellular DNA. In other words, it is possible to attribute DNA to those inducers that activate plant resistance to viruses de novo.
[0207] Thus, it has been established that GXM induces resistance of supersensitive tobacco plants to the action of viral infection de novo, because this resistance is sensitive to the action of actinomycin D. On the one hand, its activity is similar to the action of previously studied sulphated polysaccharides and yeast RNA; on the other hand, the activity is similar to neutral polysaccharides that activate the supersensitive mechanism on the basis of the protein-carbohydrate interaction.
[0208] Taking into account that the mechanism of natural and induced resistance in plants, on the whole, has not been studied comprehensively, the search of substances capable of increasing natural virus resistance is promising. In our opinion the results of such studies have importance, as polysaccharides and also glycoproteins can be use in the future as a model of endogenous triggers that is involved in activation of AVR in supersensitive plants. Such substances will also be interesting for practical application with the purpose to decrease lesions of viral infections in agricultural and decorative plant growing.
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New and distinct varieties of higher Basidiomycetes mushrooms selected from Coprinus comatus HAI-1237 and Tremella mesenterica HAI-17 deposited under The Budapest Treaty with the Centralbureau voor Schimmelcultures (CBS) under Accession Nos. CBS 123401 and. CBS 123296, respectively, biomass and extracts thereof and isolated constituents such as b-glucans, fucogalactans and glucuronoxylomannans are disclosed, and their use as natural food supplements, nutraceuticals, prebiotics, beverage products, cosmetics, pet food, and agricultural insecticidal and anti-plant virus compositions
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FIELD OF THE INVENTION
[0001] This invention concerns biocides possessing fungicidal and bactericidal properties which can be used in construction, medicine and other various areas of technics in particular in compounds for preventive prolonged antiseptic treatment of premises with long stay of humans, for treatment of surfaces of constructional units including medical purposes and for synthesis of compounds which are biocompatible with tissue of an alive organism and preferably intended for external use at treatment of skin diseases, not healing wounds, trophic ulcers, burns, dermatosis, pustular diseases of a skin, inflammatory infiltrates.
Prior Art
[0002] Use of the compositions containing metals such as Ag, Au, Pt, Pd, Cu, and Zn (see H. E. Morton, Pseudomonas in Disinfection, Sterilisation and Preservation, ed. S. S. Block, Lea and Febider 1977 and N. Grier, Silver and its Compounds in Disinfection, Sterilisation and Preservation, ed. S.S. Block, Lea and Febider, 1977) is widely known in practice of manufacture of fungicides and bactericides. It is also known that particles of substance having a size in the range of 1-100 nanometers change their chemical, physical and biological properties, which parameters have the important applied value. Even so significant attention has been recently paid to use of ultradisperse colloidal systems of biocidal preparations on the basis of metallic components, preferably silver, which are relevant to the most effective antimicrobic means (see Blagitko E. M., etc. <<Silver in medicine>>, Novosibirsk: “Science-Center”, 2004, 256 pages). In the technical specification of Russian Patent No. 2259871, a preparation possessing fungicidal and bactericidal properties received as a colloidal solution of a nanostructural composition of biocide on the basis of metals nanoparticles is described. The nanostructural composition of biocide is obtained by dissolution of metal salt and water-soluble polymer in water and/or in non-aqueous solvent. Then a reaction container with the received solution is blown through with gaseous nitrogen or argon and irradiated with radioactive radiation. In this method the reducer is a solvated electron generated by ionizing radiation in the solution. As salt of metal it is possible to apply a salt of at least one metal chosen from silver, copper, nickel, palladium or platinum. It is preferable to apply a salt of silver, for example nitrate, perchlorate, sulfate or acetate. As polymer polyvinylpirrolidone, copolymers of 1-vinylpirrolidone with acrylic or vinylacetic acids with styrene or with vinylic alcohol are used. As non-aqueous solvent it is possible to use methanol, ethanol, isopropyl alcohol or ethylene glycol. If emulsion is obtained surface-active substance is entered in the reaction container in addition. Obtained nanocomposite of biocide on the basis of metal-polymer is used as antibacterial, sterilizer or deodorizing means.
[0003] However the known method of obtaining a biocide is rather difficult and expensive as synthesis is carried out in an atmosphere of inert gas and with the use of a source of ionizing radiations for the purpose of preventing collateral reactions.
[0004] In the technical specification of Russian Patent No. 2088234.1997, the water-soluble bactericidal composition which contains in the structure nanoclusters of zero-valent metallic silver with the sizes 2-4 nanometers and poly-N-vynilchlorridone-2 is suggested. In the declared method poly-N-vynilchlorridone-2 acts not only as the stabilizer of colloidal silver but also as the reagent participating in restoration due to its end aldehydic groups. Thus ionic silver is restored up to molecular state by action of ethanol on the ions of silver coordinated with poly-N-vynilchlorridone-2. In absence of the last component, nitrate of silver does not react with ethanol. The compound is easily dissolved in water with formation of a colloidal solution and can be used for the manufacture of preparations for medicine and veterinary field. The preparation is characterized by the lowered toxicity and allergenicity.
[0005] However the method of obtaining this preparation is laborious and requires big power inputs as the technology of manufacturing provides for dispersion drying equipments; has also restriction of the raw-material base. Synthetic polymer increases cost of the preparation.
[0006] From the invention of Russian Patent No. 227866 it is also known to add a water solution of silver salts with contents from 0.0011 up to 0.40 g (from 0.007 up to 2 mmole) to a water solution of arabinogalactan at intensive randomization. Further it is kept at room temperature for 30-90 minutes. After that, 30% ammonium or sodium hydroxide is added up to pH 10-11. The obtained mixes are kept at a temperature of 20-90° C. for 5-60 minutes. The solution is filtered and target products are isolated by decantation of a filtrate in ethanol. The deposit is filtered and dried in vacuum. The contents of silver in the obtained compounds is determined with the method of the atomic-absorption analysis and varies within 3,3-19,9% depending on the conditions of reaction. Silver is in a zero-valent condition according to the data of the roentgen-diffractional analysis. Silver derivatives are generated as nanosized particles of 10-30 nanometers. These particles are water-soluble and can be isolated in a solid state. Silver derivatives of arabinogalactan possess antimicrobic properties and have a wide spectrum of uses. For example, derivatives with the various contents of silver can be used in medicine as antiseptic means of external use, as an alternative medical product to antibiotics and also as components of bactericidal coatings.
[0007] However use of the stabilizer, i.e. natural polysaccharide of arabinogalactan as a reducer of silver ions up to a zero-valent condition and also simultaneously as the reaction dispersive environment increases costs of preparation.
[0008] Thus, above mentioned technical solutions for obtaining preparations possessing bactericidal properties on a basis of nanostructural compositions of biocides are characterized by labour-intensiveness and at the same time by rather low stability of their liquid dispersions, owing to washing away or complex formation of free ions of silver in a solution.
[0009] The technical solution under Russian Patent No. 2330673 is the most close to the present invention. In this patent the nanostructural composition of biocide possessing fungicidal and bactericidal properties is disclosed.
[0010] According to the known technical solution the composition of biocide as nanoparticles of a bentonite powder intercalated by ions of Ag + or /and of Cu 2+ which are obtained with the process of modification of bentonite semi-finished products by 10-20% solutions of inorganic salts of silver nitrate or copper sulfate is disclosed. Bentonite semi-finished products are preliminarly enriched with cations of Na + by their treatment with water solution of inorganic salts of sodium bentonite in Na + form with subsequent their cleaning from acid anions after their enrichment, and from salts of sodium after the process of intercalation.
[0011] According to the known technical solution the nanostructural composition of biocide contains a basis of polar solvents.
[0012] The known nanostructural composition of biocide as nanoparticles of the bentonite powder intercalated by ions of Ag + or /and of Cu 2+ is obtained from mineral and ecologically safe components. They are biologically compatible with tissues of living organisms. The nanostructural compositions also can be used as additives for manufacturing dry building mixes, in medicine and veterinary science for antimicrobic treatment of the injured zones of tissues of living organisms, in structure of various ointment bases or of gels capable of absorbing microbic and tissues toxins.
[0013] The known nanostructural compositions of biocide can be used as a preparation, for example, for antimicrobic and fungicidal treatment of surfaces of various constructional products, for treatment of textile products and also in medicine and veterinary science for treatment of the injured zones of tissues of living organisms and in structure of preparations capable of absorbing microbic and tissues toxins.
[0014] It follows from the used technical solution that use of nanostructural compositions of biocide as a mix of nanoparticles of a bentonite powder intercalated by ions Ag + and ions Cu 2+ is the most reasonable economically. Thus, obtained biocide forms an effective synergetic composition with bactericidal and fungicidal properties.
[0015] It also follows from the applied technical solution, that bactericidal and fungicidal activity of prolonged action of biocide at treatment of surfaces of constructional products is most effective in the presence of a liquid environment, as polar solvents in the structure of the biocide. The liquid environment is safe ecologically and toxicologically. The presence of the liquid environment in a composition of biocide improves the process of its distribution on the treated surfaces, providing the maximal microbiological efficiency that is desirable at industrial application.
[0016] However compositions of biocide on the basis of a mix of nanoparticles of a bentonite powder intercalated by ions Ag + and ions Cu 2+ do not possess universality owing to possible allergenicity of tissues of living organisms at external use, in particular at treatment of never-healing wounds, trophic ulcers, burns, dermatosis, pustular diseases of a skin of patients with diabetes.
[0017] Use of nanoparticles of a bentonite powder intercalated by ions Cu 2+ can lead to formation of electrochemical corrosion in technical means and preparations intended for treatment of surfaces of constructional products, for example, made of such metals as iron and aluminium. It also can lead to biocorrosion at its use in the products protecting wood building materials from affection by fungus, for example, telephone columns, fencings, wooden floors, braided products, windows and doors, plywood, pressed wood slabs, wafer slabs, wood-shaving slabs, joiner's products, bridges or the wooden products usually used in construction of residential buildings and other constructions.
[0018] Specifically in the applied technical solution the wide range of dispersion of nanoparticles of a bentonite powder is technologically inefficient at their compounding into liquid basis owing to possible agglomeration of nanoparticles. It reduces reliability of bactericidal and fungicidal properties of the applied composition of biocide concerning various steady forms of microorganisms and colonies of mycelial fungus.
SUMMARY OF THE INVENTION
[0019] Technical result of the invention is the creation of nanostructural compositions of biocide. Thus the biocide is composed by a mix of nanoparticles of a bentonite powder intercalated by ions of metals, in a given weight ratio. This mix forms an inexpensive low toxic synergetic composition with effective bactericidal and fungicidal activity of prolonged action.
[0020] Technical result of the invention is the creation of the profitable nanostructural compositions of biocide possessing prolonged highly effective fungicidal and bactericidal properties for obtaining preparations intended for treatment of surfaces of constructional products without dependence from the physical-mechanical properties of these materials.
[0021] Technical result of the invention is the creation of profitable nanostructural compositions of biocide for obtaining preparations possessing prolonged, highly effective fungicidal properties concerning various steady forms of colonies of mycelial fungus.
DETAILED DESCRIPTION OF THE INVENTION
[0022] For the solution of the described technical problem a nanostructural composition of a biocide formed of nanoparticles of a bentonite powder, intercalated by ions of Ag + or/and by ions of Cu 2+ was suggested. These nanoparticles are obtained with a process of modification of bentonite semi-finished products by 10-20% solutions of inorganic salts of silver nitrate or copper sulfate. Bentonite semi-finished products are preliminarly enriched with cations of Na + by treatment with a water solution of inorganic salt, of a sodium bentonite in Na + form, with subsequent its cleaning from acid anions, after enrichment, and from salts of sodium after the process of intercalation. The composition of the present invention is different in that nanoparticles of bentonite powder intercalated by ions of Zn 2+ are additionally entered in the above said composition. These nanoparticles are obtained by treatment with 10-20% solutions of inorganic salts preferably of chloride zinc (ZnCl 2 ) or sulfate zinc (ZnSO 4 ), after the process of modification by enrichment with cations of Na + of said bentonite semi-finished products, with subsequent their cleaning from sodium salts and dispersion.
[0000] The new composition has the following ratio of components (weight parts):
[0023] nanoparticles intercalated by ions of Ag + : nanoparticles intercalated by ions of Zn 2+ as 1:(0,2 −0,8);
[0024] or
[0025] nanoparticles intercalated by ions of Ag+: nanoparticles intercalated by ions of Zn 2+ : nanoparticles intercalated by ions of Cu 2+ as 1:(0,2 −0,8):(0,2−0,5);
[0026] or
[0027] nanoparticles intercalated by ions of Zn 2+ : nanoparticles intercalated by ions of Cu 2+ as 1: (0,2 −0,5),
[0000] and dispersion of nanoparticles of bentonite powders of no more than 70 nm.
[0028] According to the invention the composition of biocide may contain a liquid basis of polar solvents.
[0029] According to the invention, solutions of the named inorganic salts of silver, copper and zinc are used to modify of semi-finished products of bentonite enriched with ions Na + in the hereinafter specified weight ratio: semi-finished product:solution as 1:(10−40).
[0030] By realization of the claimed technical solution the creation of an inorganic biocide with the structure of a mix of nanoparticles of a bentonite powder intercalated by ions of said metals in the given weight ratio is ensured. It forms an inexpensive synergetic composition with highly effective bactericidal and fungicidal prolonged action on treated zones of tissues with antiallergenic effect.
[0031] By realization of the claimed technical solution, creation of the nanostructural compositions of biocide as inexpensive synergetic compositions on the basis of nanoparticles of a bentonite powder intercalated by ions of metals and of a polar solvent is provided. This composition provides highly effective bactericidal and fungicidal prolonged action on surfaces of various constructional products without dependence on physical-mechanical properties of materials, forms of microorganisms and colonies of mycelial fungus.
[0032] The obtained technical result of the invention is explained in the following way:
[0033] use of a natural mineral as bentonite in Na-form for manufacturing the preparation, whose structure is characterized by a crystal lattice with typical disposition of “packages” as level-by-level. The “packages” are represented as negatively charged aluminium-oxygen and silicon oxygen compounds where the volume of interlayer space has high sorption activity to solutions and to reaction of ionic replacement of cations of one metal with cations of other metals at presence of solutions with cations of metal-substituent in interlayer space;
[0034] performing of preliminary enrichment of bentonite in Na-form with ions Na + . It provides activation of bentonite owing to increase in total quantity of Na + ions in its exchange capacities. They are capable of further ionic exchange at technological operations of intercalation of the ionic processes accompanying by reaction of replacement of adsorbed sodium cations on cations of other metals in exchange capacities of bentonite. As a result of reactions of ionic exchange at modification of bentonite by solutions of salts of silver nitrate (AgNO 3 ), copper sulfate (CuSO 4 ), salt of zinc (ZnCl 2 ), the density of Ag + ions, Cu 2+ ions, Zn 2+ ions mainly in the interlayer space of aluminium-oxygen and silicon oxygen compounds of bentonite is raised. Processes of activation of bentonite clays due to their enrichment by ions of corresponding metals (technological treatment by salt solutions) in particular by ions of Na + , are used in the dehydration of cellulose masses, dehydration of paper sediments during differentiation between a liquid/firm body, in the cleaning of sewage, cleaning of water with the waste products containing inks and in the fixing of a pitch (during manufacture of paper) and also when obtaining bentonite for granulation of iron ore or for treatment of other minerals;
[0035] use of biocide dispersive environment of nanoparticles of a bentonite powder with a high specific surface in the nanostructural compositions. It provides the big area of contact to the bacterial environment and raises efficiency of antimicrobic and fungicidal influences on pathogenic microflora;
[0036] presence of nanoparticles intercalated by ions of Zn 2+ with inhibitors of corrosion - in biocide;
[0037] presence of nanoparticles of a bentonite powder intercalated by ions of Zn 2+ in the composition biocide. Nanoparticles promote favorable antibacterial influence on tissues of homoiothermal organisms. It is widely known practice the use of Zn-containing preparations improving live ability of living organisms in medicine and in veterinary science;
[0038] use of synergetic compatible components both on the basis of mixes of bentonite powders intercalated by ions of metals and on the basis of applied liquid environment in the nanostructural compositions of biocide. They are ecologically safe to various work surfaces;
[0039] decrease in costs of obtaining a biocide due to the use of a high dispersion, synergistically compatible mix of nanoparticles of bentonite powders in its composition;
[0040] At the analysis of expert technics, it was not revealed a technical solution with a set of attributes corresponding to the technical solution according to the invention and able to realize the above described result of prolonged action of bactericidal (antimicrobic) and fungicidal efficiency on work surfaces of various constructional products and tissues of homoiothermal organisms.
[0041] The presented analysis of the state of the art testifies the conformity of the declared technical solution to criteria ornovelty” and “inventive level”.
[0042] The technical solution according to the invention can be realized industrially for obtaining the preparations intended, for example, for antimicrobic treatment of wound, burn, ulcer zones of skin integuments, for treatment of mucous surfaces of the oral cavity, for preventive and for prolonged antimicrobic and fungicidal treatment of surfaces of the constructional products made of various materials.
[0043] The essence of the invention is explained in the following way:
[0044] tables 1 and 2 expose the results on bactericidal and fungicidal efficiency of nanostructural compositions of biocide according to the invention;
[0045] recommendations concerning the choice of source of raw materials for manufacturing of the nanostructural compositions of biocide possessing fungicidal and bactericidal properties.
[0046] For obtaining of the nanostructural compositions of biocide possessing fungicidal and bactericidal properties, finished medical and laboratory equipments, commodity products and also known technological processes are used, in particular:
[0047] bentonite (montmorillonite) in Na-forms, for example, Sariguh deposit (Armenia) with alkaline bentonites in which contents of montmorillonite (bentonite in Na-forms) is 75-85 mass %. That is the most preferable to realization of the technological process of obtaining a biocide;
[0048] silver nitrate (AgNO 3 ); copper sulfate (CuSO 4 ); zinc chloride (ZnCl 2 ) or zinc sulfate, sodium chloride (NaCl);
[0049] deionizided water; alcohol, preferably isopropyl alcohol. The specified solvents accordingly water and alcohols concern the class of polar solvents.
[0050] the nanostructural composition of biocide possessing fungicidal and bactericidal properties (see Russian Patent No. 2330673, with a priority date of 22.11.2006, Patent holder—Joint-Stock Company <<Institute of Applied Nanotechnology>>). According to it mineralogical raw material (bentonite in Na-forms) is activated (enriched) by ions of Na + , by treating it with 3-10% water solution of sodium chloride, subsequent washing and filtering of the obtained semi-finished product for removal of acid anions. Then the obtained semi-finished product is modified by 10-20% solution of inorganic salts of metal such as silver nitrate (Ag NO 3 ) or copper sulfate—Modified bentonite is kept to mature in the specified salt solutions and then modified bentonite is cleaned from salts of sodium by washing and filtration and, after drying, the obtained preparation is reduced to powder. Thus treatment of an inorganic mineral by the named solutions is made at a ratio—weight parts of bentonite:solution as 1:(10−40).
[0051] Obtaining of the nanostructural composition of biocide, possessing antimicrobic prolonged action on a colony of bacteriological impurity and organisms, is provided at realization of the applied invention on the basis of use of the components mentioned above, of the known technological processes and with the specified weight ratio of components.
[0000] These industrial applications are typical:
[0052] for treatment of surfaces of constructional products without dependence on physical-mechanical properties of their materials;
[0053] for treatment of various infected wounds including not healing for a long time and not reacting to treatment with known means.
[0054] Nanostructural compositions of biocides obtained according to the invention are not toxic, do not cause an allergy, have no contra-indications and possess high antiedematous, sorption, ion-exchanging and antiinflammatory properties.
[0055] Realization of the invention with change of structure of the used components and of the specified weight ratio, will lead to worsening of properties of the provided biocide compositions or to increase in cost of process for their obtainment.
Experimental Part
[0056] Realization of the invention is explained by the following steps and concrete examples of its implementation:
[0057] 1st step—manufacturing of semi-finished products of bentonite preliminarly enriched with cations of Na + . According to it, semi-finished products are obtained with the technological process of the Russian Patent No. 2330673:
[0058] Bentonite (montmorillonite) in Na-form in amount of 5 g, is coated preferably with 5% water solution of NaCl and kept in the given solution. Thus additional enrichment of bentonite by ions of sodium is carried out. Then the obtained compound is washed for removal of chlorine anions, subsequently filtered through the filter <<a white tape>> and dried.
[0059] 2nd step—obtaining of nanoparticles of a bentonite powder intercalated by ions of metals, without containing salts of sodium.
[0060] Nanoparticles of the bentonite powders without salts of sodium from semi-finished products of bentonite made at 1st step, are obtained according to the following examples:
EXAMPLE 1
[0061] A semifinished product was cleaned from acid anions, dried up and modified by 10-20% water solution of silver nitrate (at red illumination). It was preferable to apply 15% water solution of silver nitrate. The process of modification was carried out at its keeping in the specified solution and at a temperature corresponding to its solubility in water. The obtained modified semi-finished product was repeatedly washed out for removal of sodium salts; filtered and dried preferably at a temperature higher than 200° C. and no more than 800° C. The consumption of water solutions for the treatment of 5 g semi-finished product was of bentonite : water solution as 1 : 20. After drying, the product was reduced to dispersed powder. A bentonite powder without salts of sodium and intercalated by ions of Ag + was obtained. A useful yield of the product was 4.8 g
EXAMPLE 2
[0062] The same materials and technological method as in the example 1 were used, but modification of bentonite enriched by ions of sodium, was carried out with use of 15% water solution of copper sulfate. A bentonite powder without salts of sodium and intercalated by ions of Cu 2+ was obtained. A useful yield of the product was 4.8 g
[0063] Nanostructural compositions of biocides of Examples 1 and 2 were obtained according to the known process protracted by the Russian patent No. 2330673.
[0064] Nanoparticles of a bentonite powder intercalated by ions of Zn 2+ to be inserted in the nanostructural compositions of biocide of the present invention, were obtained according to following Example 3.
EXAMPLE 3
[0065] The same materials and technological methods as in the Example 1 were used, but modification of a semi-finished product of bentonite enriched by ions of sodium was carried out according to the present invention. For these purposes it was used 10-20%, preferably 15%, water solution of chloride zinc (ZnCl 2 ) (the most accessible chemical preparation). In result, after repeated washing for removal of sodium salts, filtering, drying and subsequent reducing to dispersed powder, a bentonite powder without salts of sodium and intercalated by ions of Zn 2+ was obtained. A useful yield of the product was 4.8 g
[0066] The consumption of the salt of water solution for the treatment of 5 g semi-finished product was: bentonite:water solution as 1:20.
[0067] Process of dispersing powders of the invention up to the specified dispersion of nanoparticles is carried out in all Examples as follows:
[0068] The obtained products after intercalation (modification) by ions of metals, their cleaning from salts of sodium and drying, are slurried (intensively mixed) in plenty of water and are allowed to settle during some time. The decanted product is slurried in additional portion of water the deposit is slurried, settled and decanted again. This process is carried out ,repeatedly. By filtration from decanted liquids a nanodispersion product is isolated. Then it is dried and grinded in planetary mills. A plenty of deionized water is used in such a way of obtaining nanopowders. The process is rather long.
[0069] For reducing the time of processing to nanoparticles, the named products of Examples 1-3 were compounded in deionized water at the following ratio of weight parts: a product (Examples 1-3): solvent as 1:10. Then it was carried out formation of a dispersion of nanoparticles of the bentonite powder up to the dimension of them of no more than 70 nm, with use of ultrasonic dispersant.
[0070] Ultrasonic dispersant are widely used in various industries (chemical, pharmaceuticals, food, etc.). As a source of ultrasound either hydrodynamical radiators or radiators on the basis of electro-mechanically active materials are used, for example, magnetostrictive converters. Use of ultrasonic dispersant will considerably speed up the process of structuring bentonite powders up to the specified value of dispersion.
[0071] In a case the process was carried out with use of dispersant Bandelin Sonoplus HD2070 at capacity 40 Watt for 10-20 minutes. Obtained colloidal systems were deposited on a sublayer and after evaporation of water were scanned by a microscope.
[0072] The control of dimension of obtained dispersion of bentonite powders was made with use of an electronic microscope. As a result of the carried out technological methods, dispersion of nanoparticles to less than 70 nanometers was obtained, with the following distribution: dispersion of 30% from total structural product was of 5-20 nanometers, the rest was less than 70 nm.
[0073] Dispersions of bentonite powders, intercalated by ions of the named metals, with dimension of nanoparticles less than 70 nm were used for the preparation of mixes of the nanostructural compositions of biocide of the invention:
EXAMPLE 4
[0074] Obtained nanoparticles of the bentonite powders intercalated by ions of Ag + and Zn 2+ (Examples 1 and 3) were mixed at a ratio of their weight parts of:
[0075] the product of Example 1 : the product of Example 3 as 1:0, 5.
[0076] Obtained mix of nanoparticles of bentonite powders was compounded into polar solvent preferably into deionized water at the following ratio:
[0077] Mix of bentonite powders of Example 4:polar solvent as 1:20.
[0078] 5% liquid solution of the composition of biocide is obtained.
EXAMPLE 5
[0079] Obtained nanoparticles of bentonite powders intercalated by ions of Ag + , Zn 2+ and Cu 2+ (Examples 1, 2 and 3) were mixed at a ratio of their weight parts of:
[0080] the product of Examplel : the product of Example 3: the product of Example 2 as 1:0, 5 : 0,3.
[0081] Obtained mix of nanoparticles of bentonite was compounded into polar solvent preferably into deionized water, at the following ratio:
[0082] Mix of bentonite powders of Example 5: polar solvent as 1:20.
[0083] 5% liquid solution of the composition of biocide is obtained.
EXAMPLE 6
[0084] A mix of nanoparticles of bentonite powders as used in Example 5 was compounded in a polar solvent as 40% of a hydro-alcoholic solution, at the following ratio of weight parts:
[0085] the product of Example 5: solvent as 1:20
[0086] 5% liquid solution of the composition of biocide is obtained.
EXAMPLE 7
[0087] Nanoparticles of bentonite powders intercalated by ions of Zn 2+ and Cu 2+ according to Examples 2 and 3, were mixed at a ratio of weight parts of:
[0088] the product of Example 3: the product of Example 2 as 1:0, 5
[0089] The mix of nanoparticles of bentonite powders was compounded into deionized water at the following ratio:
[0090] mix of bentonite powders of Example 7: polar solvent as 1:20
[0091] 5% liquid solution of the composition of biocide is obtained.
[0092] Control compositions of biocides have been prepared additionally for carrying out comparative tests of Examples 8 - 10:
EXAMPLE 8
[0093] The product of Example 1: polar solvent (deionized water) as 1:20
EXAMPLE 9
[0094] The product of Example 2: polar solvent (deionized water) as 1:20
[0095] In all examples 1-9 used nanoparticles of bentonite powders had dispersion of no more than 70 nm.
EXAMPLE 10
[0096] The product of Example 1: polar solvent (deionized water) as 1:20,
[0097] dispersion was no more than 100 nm (dispersion of 30% of nanoparticles was no more than 30 nm and dispersion of 70% was 100 nm).
[0098] Biocidal properties of the preparations obtained in accordance to Examples 1-10 were estimated on bactericidal and fungicidal activity of tested samples.
[0099] Estimation of bactericidal (antimicrobic) activity of nanostructural compositions of tested samples was carried out with use of an integrated disk-diffusion method. (the Directions on medical microbiology. General and sanitary microbiology. Under edition of A. S. Labinskaya, E. G. Volina. Moscow, BINOM, 2008, pages 342-352.)
[0100] The specified method is based on diffusion of a tested antimicrobic preparation in a dense nutrient medium.
[0101] The method consisted in unitary treatment of standard disks in diameter of 5 mm by tested samples.
[0102] Disks were placed on the surface of a dense nutrient medium (a tripkazo-soy agar (TSA) manufactured by bioMerieux, France) preliminarly inoculated by one of test-microorganisms.
[0103] Petri's cup with cultures of test-microorganisms and the disks treated with water solutions of samples were placed in thermostat for 24-48 hours at a temperature of 37° C.
[0104] After the expiration of the specified term, results of the research were determined by measurement of diameter of a zone of a growth delay of test-microorganisms in mm around of the disks. Each research was repeated three times.
[0105] 24-hour cultures of bacteria of Staphylococcus aureus, Pseudomonas aeruginosa and spores of bacteria of Bacillus cereus were used as test-microorganisms.
[0106] For preparation of a suspension of test-culture of spore—generating bacteria the daily culture was used, grown up on a dense nutrient medium (a tripkazo-soy agar) at a temperature of 37° C. Then suspension of culture in a physiological solution was prepared for stimulation of spore—generating at bacteria of sort Bacillus . It was dispersed on a surface of a potato agar poured in sterile Petri's cup in volume of 0.2-0.5 ml on a cup. Incubation period was in thermostat for 48 hours at a temperature of 37° C. After incubation Petri's cup with plating microorganisms were pulled out from thermostat and kept at room temperature (20-22° C.) in the presence of a natural light source for 5 days.
[0107] Further control was carried out on test-cultures of bacteria which have been grown up on a potato agar for 7 days under various conditions of incubation. This research was directed to reveal spore-generating bacteria of sort Bacillus . For this purpose a preparation of test-culture of bacteria was prepared, it was painted over by the method of Shaffer-Fulton and examined under a microscope. If about 90-95° A, spores of bacteria are visible at survey of the preparation under a microscope, the preparation of the spore-generating test-culture could be used for preparation of a suspension. Otherwise the test-culture of bacteria needs further incubation.
[0108] A suspension of each test-culture of bacteria was prepared in a sterile physiological solution using the reference glass standard of turbidity on 10 units. It corresponds to an amount of microbic cells of 1 billion/ml. Then the concentration of a suspension of test-microorganisms equal to 10 6 cells in 1 ml by series of consecutive cultivations in a sterile physiological solution was obtained. The suspension of each kind of bacteria with the specified concentration was deposited on the surface of a nutrient medium. On the obtained bacterial area the disks impregnated with the researched preparations according to examples 4-10, were imposed.
[0109] Bacteria of Staphylococcus aureus are chosen as one of the most resistant representatives of the gram-positive microflora of the human being. Besides, they are one of the basic activators of hospital infections and also activators of pustular infections of a skin, furuncles, abscesses and other complications.
[0110] Bacteria of Pseudomonas aeruginosa (strain ATCC No. 10145) are chosen as one of the most resistant representatives of the gram-negative flora possessing high stability to physical and chemical factors. As a rule, they show resistance to many medicinal and to disinfectants. Besides, bacteria of the given kind are known as activators of infectious complications of bum wounds, bacteremias, septicemias with a fatal outcome and other complications of infectious aetiology.
[0111] Bacteria of Bacillus cereus (strain No. 8035 NCTC) are chosen as representatives of spore-generating microorganisms which spores are the steadiest to be influenced by adverse factors of an environment including action of disinfectants. Both activators of infectious diseases and activators of biocorrosion of constructional materials are available among them. As a rule, spores of bacteria of Bacillus are used for tests of work of autoclaves, dry-heating cases and disinfectants.
[0112] Results of the carried out researches are submitted in the Table 1. Estimation of fungicidal (antifungicidal) activity of tested samples (Examples 4-10) was carried out with an integrated disk-diffusion method as mentioned above.
[0113] The method consists in unitary treatment by tested samples of standard disks in diameter of 5 mm.
[0114] Disks were placed on the surface of a dense nutrient medium (Czapek Dox agar manufactured by Himedia, India) preliminarly inoculated with one of test-microorganisms.
[0115] Petri's cup with cultures of test-microorganisms and the disks processed with the mentioned samples were placed in thermostat for 5-7, 24 hours at a temperature of 28° C.
[0116] After the expiration of the specified term the result of researches were determined by measurement of the diameter of a zone of a growth delay of tests-microorganisms in mm around the disks.
[0117] A number of samples of each sort was taken in view of carrying out an estimation of each parameter at least on 3 samples.
[0118] As test-microorganisms cultures of fungus of Aspergillus sydown (pieces 9-6), Aspergillus niger (pieces 4-3-11), Cladosporium cladosporioides pieces (2-3), Penicillium expansum (pieces 4-3-3), Ulocladium botrytis (pieces 15-10) were used. These strains have been isolated from an inhabitancy of the International space station and possessed stability to the influence of adverse factors of an environment including the action of disinfectants. As a rule fungus of Aspergillus niger are used for tests of disinfectants.
[0119] For standardization of test-cultures, strains were grown in Petri's cup with the medium of Capek. Their specific identity was confirmed on the basis of the analysis of their cultural and morphological properties. Then they were placed on the oblique agar (Capek's medium) poured out in big test tubes (diameter of 20-22 mm). Cultures were grown in thermostat at a temperature of 28° C. for 10-14 days. Strains thus obtained were kept in a refrigerator at a temperature of +4° C. and, as required they were placed out and used for preparation of a suspension. For preparation of a suspension of fungus strains the test-cultures of fungus were used. They had been grown up in Capek's medium at 28° C. at ages from 14 till 28 days beginning from the moment of plating.
[0120] Suspension of strains in concentration of 1 million/ml was prepared separately for each kind of test-cultures of fungus. For this purpose strains of fungus from a test tube with pure culture were transferred in a flask (test tube) containing 15±5 ml of a sterile physiological solution. Transfer of strains from test tubes in a flask (test tube) was made by the method of holding of strains by a bacteriological loop.
[0121] At intake of strains from a test tube a nutrient medium was not touched by a loop. Determination of amount of strains in suspension was carried out by a method of calculation with use of accounting chamber of Gorjaeva.
[0122] Suspension of every kind of fungus with the specified concentration was placed on the surface of a nutrient medium (a lawn of culture). On the obtained lawn of fungus the disks impregnated by researched samples (Examples 4-10) were placed.
[0123] Results of the carried out researches are submitted in the Table 2.
[0124] From the analysis of the Tables 1 and 2 it results what follows:
[0125] Water and hydroalcoholic solutions of nanostructural compositions of biocide (examples 4-10) possess antimicrobic activity in respect to representatives of gram-positive, gram-negative and spore-generating flora (Table 1).
[0126] It follows from the Table 1 that testing samples (Sample 8) containing nanoparticles of bentonite intercalated by ions of silver (Ag + ), zones of a growth inhibition around of the disks with bacteria of S. aureus was 20 mm, with bacteria of P. aeruginosa was 18 mm and with spore-generating bacteria of B. cereus was 11 mm. These data testify the efficiency of bactericidal activity of silver preparations. It is known for the given kind of metal possessing a wide spectrum of antimicrobic activity. At the same time it is known that costs for manufacturing the given product are considerably high and thus inexpedient.
[0127] As a result of tests it is also determined that tested samples according to the invention (Samples 4-7), containing a mix of nanoparticles of bentonite with ions of metals according to the invention, insignificantly differ from the product of the Sample 8 for the bactericidal properties of prolonged action. And in comparison with it, costs for obtaining samples 4-7 are lower.
[0128] As a result of the tests it is also determined that significant growth of Bacillus ( Bacillus cereus strain No. 8035 NCTC) took place by using a composition of biocide on the basis of nanoparticles of a bentonite powder intercalated by ions Cu 2+ (Sample 9). That testifies the presence of biocorrosion processes.
[0129] It is also determined that the efficiency of bactericidal properties of preparations according to the invention (Sample 10), considerably decreases in the presence of product with significant part of nanoparticles of bentonite powders with dispersion of more than 70 nm.
[0130] The best fungicidal properties were shown by preparations of Examples 4-8.
[0131] Fungistatic and fungicidal properties were determined in these preparations. They showed a different degree of influence of their activity on various kinds of fungus (Table 2). The most sensitive to the specified tested preparations were dark-colored fungus showed and the most resistant funguses were aspergillus . It follows from researches on estimation of fungicidal (antifungicidal) activity, that tested samples according to the invention (Samples 4-7) containing a mix of nanoparticles of bentonite with ions of metals according to the invention, insignificantly differ from the product by the Sample 8 (control example) in respect to the fungistatic and fungicidal properties of prolonged action. And in comparison with it, costs for obtaining Samples No. 4-7 are lower.
[0132] It is also determined that efficiency of fungicidal properties of preparations (Sample 10) considerably decreases at dispersion of nanoparticles of bentonite powders more than 70 nm.
[0133] Thus, the carried out researches as a whole confirm high efficiency of bactericidal and fungicidal properties of prolonged action of nanostructural compositions of biocide to various colonies of microorganisms under the applied invention, what testifies the expediency of use of the invention for the following purposes:
[0134] for antimicrobic treatment of wounded, burn, ulcer zones of integuments, for treatment of mucous surfaces of the oral cavity without intoxication of treated zones;
[0135] for treatment of surfaces of constructional products without dependence from properties of the materials used for their manufacturing.
[0000]
TABLE 1
Antibacterial activity of test samples
Type
Staphylococcus
Pseudomonas
Bacillus
aureus
aeruginosa
cereus
Diameter of a zone of a growth inhibition
of tests-microorganisms around of standard
disks processed by tests samples in mm.
No.
Tested samples
Disk diameter - 5 mm.
1
Sample 4
18
17
10
(Ag + + Zn 2+ + water)
2
Sample 5
19
17
10
(Ag + + Cu 2+ +Zn 2+ +
water)
3
Sample 6
(Ag + + Cu 2+ +Zn 2+ +
20
18
11
hydroalcoholic basis)
4
Sample 7
17
16
9
(Cu 2+ + Zn 2+ + water)
5
Sample 8
(Ag + + water)
20
18
11
reference sample
6
Sample 9
(Cu 2+ + water)
14
11
6
reference sample
7
Sample 10
(Ag + + Cu 2+ + Zn 2+ +
12
10
7
water)
[0000]
TABLE 2
Fungicidal properties of test samples
Type of tests-culture
Aspergillus
Aspergillus
Cladosporium
Penicillium
Ulocladium
sydowii
niger
cladosporioides
expansum
botrytis
Diameter of a zone of a growth inhibition of tests-
microorganisms around of standard disks processed by
No.
Tested samples
tests samples in mm. Disk diameter - 5 mm.
1
Sample 4
0
0
4
2
2
(Ag + + Zn 2+ + water)
2
Sample 5
0
1
5
2
2
(Ag + + Cu 2+ + Zn 2+ + water)
3
Sample 6
0
1
5
2
2
(Ag + + Cu 2+ + Zn 2+ +
hydroalcoholic basis)
4
Sample 7
0
0
4
2
2
(Cu 2+ + Zn 2+ + water)
5
Sample 8
0
0
5
2
2
(Ag + + water)
6
Sample 9
0
—
2
0
1
(Cu 2+ + water)
7
Sample 10
0
0
2
1
1
(Ag + + Cu 2+ + Zn 2+ + water)
(—) - in 5 days growth if the test-culture of funguses ( Aspergillus niger ) on the disk is exposed;
(0) - in 5 days the test-culture does not grow on the disk.
|
This invention concerns biocides possessing fungicidal and bactericidal properties which can be used in construction, medicine and other various areas of technics. A nanostructural composition of biocide is realized from nanoparticles of bentonite powders intercalated by ions of Zn2+ and ions of Ag+ and/or ions of Cu2+. The biocides according to the invention are prepared starting from bentonite poweder which is preliminarly enriched with cations of Na+, then treated with 10-20% solutions of inorganic salts of Zn (preferably zinc chloride or zinc sulfate ZnSO4), and from bentonite powders preliminarly enriched with cations of Na+ and then treated with 10-20% solutions of inorganic salts of at least one ion selected in the group consisting of Ag+ ions (preferably silver nitrate) and Cu2++ ions (preferably copper sulfate). The powders of bentonite, intercalated with the Zn2+, Ag+ and/or Cu2+ ions, are .cleaned from acid anions and Na+ salts, and dispersed into nanoparticles mainly of no more than 70 nm.
| 0
|
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of our application U.S. Ser. No. 816,617, filed July 18, 1977, now U.S. Pat. No. 4,133,885, issued on Jan. 9, 1979.
BACKGROUND OF THE INVENTION
Excess secretion of gastric acid can cause indigestion and stomach distress and, if prolonged, may result in ulcer formation. Treatment of excess secretion of gastric acid has heretofore consisted mainly of a bland diet, abstinence from certain foods and the use of antacids to neutralize the gastric acid after it is secreted into the stomach. An improved method of treatment would result from the inhibition of gastric acid secretion. It is thus an object of the present invention to provide compounds which inhibit gastric acid secretion. Another object is to provide methods for the preparation of these compounds. A further object is to provide pharmaceutical formulations for the administration of these compounds. Still another object is to provide a method to inhibit gastric secretion. These and other objects of the present invention will become apparent from the following description.
DESCRIPTION OF THE INVENTION
The compounds of the instant invention are best described by reference to the following structural formula: ##STR1## wherein X is sulfur or oxygen;
n is an integer of from 2 to 6 such that the length of the carbon chain connecting the two nitrogen atoms is not less than 2;
R 1 , R 2 , R 3 , R 4 and R 5 are independently hydrogen, loweralkyl, loweralkoxy, amino, haloloweralkyl or phenyl; or any two adjacent substituents may be joined to form a benzo substituent;
R 6 and R 7 are independently hydrogen, loweralkyl, phenylloweralkyl, N-loweralkylcarbamoyl, N-loweralkylthiocarbamoyl, or R 6 and R 7 may be joined to form a morpholine ring; or R 6 and R 7 may be an alkylene linkage of 4 or 5 carbon atoms to form a pyrrolidine or piperidine ring which may be substituted with loweralkyl, oxo or benzo substituents; and the broken line in the 3,4 position of the naphthyridine molecule indicates that the bond may be either a single or a double bond provided that when n is 2, R 3 , R 5 , R 6 and R 7 are all methyl groups, X is oxygen, and the 3,4-position is unsaturated, at least one of R 1 , R 2 or R 4 is other than hydrogen.
The compounds of this invention may be isolated and used as the free base or as a pharmaceutically acceptable acid addition salt. Such salts are formed by reaction of the free base with the desired inorganic or organic acid. The salts are prepared using methods known to those skilled in this art. Exemplary inorganic acids are hydrohalic acids such as hydrochloric or hydrobromic, or other mineral acids such as sulfuric, nitric, phosphoric and the like. Suitable organic acids are maleic, fumaric, tartaric, citric, acetic, benzoic, succinic, isethionic and the like.
In addition, the quaternary salts formed with the free base compounds of the foregoing structural formula and a loweralkyl halide are also considered as part of this invention. The preferred salts are prepared from loweralkyl iodides, especially methyl iodide.
In the instant specification the term "lower-alkyl" is intended to include those alkyl groups of either straight or branched configuration which contain from 1 to 6 carbon atoms. Exemplary of such alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl and the like.
The term "loweralkoxy" is intended to include those alkoxy groups of either straight or branched configuration which contain from 1 to 6 carbon atoms. Exemplary of such alkyl groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, tertiary butoxy, sec butoxy, pentoxy and the like.
The "haloloweralkyl" group is defined as a lower-alkyl group with 1, 2 or 3 halo substituents.
The term "halo" or "halogen" is intended to include the halogen atoms fluorine, chlorine, bromine and iodine.
The "N-loweralkylcarbamoyl" and "N-loweralkyl thiocarbamoyl" groups are respectively visualized as follows: ##STR2##
PREFERRED EMBODIMENTS OF THE INVENTION
The preferred embodiments of the instant invention are realized in the foregoing structural formula wherein:
X is oxygen;
n is 2, indicating an ethylene linkage;
the 3,4 bond in the naphthyridine molecule is a double bond;
R 1 , R 2 and R 4 are independently hydrogen or loweralkyl; R 3 and R 5 are independently hydrogen, loweralkyl, loweralkoxy, trifluoromethyl or amino;
R 6 and R 7 are independently hydrogen or loweralkyl; provided that when R 3 , R 5 , R 6 and R 7 are all methyl groups at least one of R 1 , R 2 or R 4 is other than hydrogen.
Further preferred embodiments of this invention are realized when:
X is oxygen;
n is 2, indicating an ethylene linkage;
the 3,4 bond in the naphthyridine molecule is a double bond;
R 1 , R 2 and R 4 are hydrogen;
R 3 and R 5 are independently hydrogen, methyl or ethyl;
R 6 and R 7 are independently hydrogen, methyl, ethyl, propyl or isopropyl provided that when R 3 and R 5 are both methyl, one of R 6 and R 7 is other then methyl.
The compounds of the present invention wherein X is oxygen are prepared by reacting a substituted 2,6-diamino pyridine with a substituted 1,3-alkanedione; converting the 2-amino naphthyridine thus prepared to the 1-unsubstituted naphthyridin-2-one by a diazotization-hydrolysis, and then alkylating at the 1-position with the substituted amino alkyl group. The reaction is outlined in the following reaction scheme: ##STR3## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and n are as previously defined, and Hal is a halogen.
In the first step of the reaction, an appropriately substituted 2,6-diamino pyridine (I) is combined with a 1,3-alkanedione (II) in phosphoric acid. In structure II, when R 3 is hydrogen the 1,3 alkanedione is a 3-oxoaldehyde and generally the reagent is employed in the form of a dialkylacetal. The mixture is heated at temperatures of from 75° to 110° C. for from 3 to 16 hours. The reaction mixture is then cooled and the product isolated using techniques known to those skilled in this art.
The 2-amino-1,8-naphthyridine (III) thus produced is converted to the diazonium salt with sodium nitrite in an acid, preferably trifluoroacetic acid or sulfuric acid. The diazonium salt is prepared at -5° C. or less during the addition, over a period of about 2 hours, of the sodium nitrite. The reaction mixture then is generally maintained at this temperature for an additional hour, and combined with a mixture of ice and water. The aqueous mixture is then made alkaline preferably with ammonium hydroxide, and the product 1,8-naphthyridine-2-(1H)-one (IV) isolated using known techniques.
This compound is then converted into the 1-substituted compound. The alkali metal salt of the 1-unsubstituted compound is first prepared, using an alkali metal hydride, preferably sodium hydride in an aprotic solvent. The preferred solvents are polar aprotic solvents such as dimethyl formamide or dioxane. The alkali metal salt is generally prepared at room temperature. In addition, the alkali metal salt may be prepared from an alkali metal alkoxide such as an alkali metal methoxide or ethoxide. The reaction is generally carried out with the alkali metal in an alcohol. The reaction is carried out at from room temperature to the reflux temperature of the reaction mixture. The alkali metal salt is generally not isolated but rather used in situ. A substituted amino alkyl halide is then added to the reaction mixture and it is heated at from 50° to 125° C. for from 3 to 24 hours. The product 1-substituted naphthyridine-2(1H)one (V) is isolated using known techniques.
The process for the preparation of the compounds of structure (V) wherein R 6 and R 7 are hydrogen involves the use of a 1-phthalimido alkyl intermediate (also a compound of this invention). The reaction proceeds as follows: ##STR4## wherein Hal is a halogen.
The reaction conditions for the preparation of the phthalimido intermediate (VI) utilize the alkali metal salt as in the preparation of compound (V). The same reaction conditions are employed except that a phthalimido alkyl halide is used as the reagent.
The phthalimido intermediate (VI) is combined in a polar solvent, such as a loweralkanol, with hydrazine and heated at reflux for from 10 minutes to 2 hours, preferably for from 1/2 to 1 hour. The reaction mixture is cooled and acidified and the product (VII) isolated usually as the addition salt with the acidifying acid. Hydrochloric acid is preferred, however, other mineral acids are acceptable.
The compounds wherein X is sulfur are prepared from those wherein X is oxygen by treatment with phosphorus pentasulfide or from hydrogen sulfide and hydrogen chloride. ##STR5##
The phosphorus pentasulfide reaction takes place in methylene chloride or pyridine at from room temperature to the reflux temperature for a period of about 4 hours. Preferably the reaction is conducted at from about room temperature to 50° C. The product is isolated using known techniques.
The reaction with hydrogen sulfide and hydrogen chloride is carried out generally in an alcohol solvent at temperatures of from 0° C. to room temperature and is complete in from 1/2 hour to 2 days.
The compounds wherein the 3,4-position bond is a single bond are prepared from the analogous double bond compound as follows: ##STR6##
The starting material (V) is dissolved in a solvent such as a lower alkanoic acid preferably acetic acid and a catalyst such as platinum oxide is added. The mixture is then agitated under an atmosphere of hydrogen, either at atmospheric pressure or pressurized. Pressures of up to 50 pounds per square inch are utilized in the normal laboratory hydrogenation apparatus. The reaction is complete when a calculated molar quantity of hydrogen has been consumed. The reaction is generally carried out at room temperature, however, heating up to about 75° C. is acceptable.
The N-loweralkylcarbamoyl and N-loweralkylthiocarbamoyl substituents for R 6 or R 7 are prepared from the compounds wherein R 6 and R 7 are hydrogen according to the following reaction scheme: ##STR7## wherein R 8 is loweralkyl and X is oxygen or sulfur.
The compounds are prepared by reacting the primary amino compound (VII) with a loweralkyl, isocyanate or isothiocyanate. The reaction is carried out in aqueous media generally at reflux temperature. The reaction is generally complete in about 10 minutes to 1 hour at reflux and the product (XI) is isolated using known techniques.
The primary amine compound (VII) is also an intermediate for an alternate preparation of the compounds wherein R 6 and R 7 are methyl groups. ##STR8##
The reaction is carried out in the presence of aqueous formaldehyde and formic acid. The reaction is generally refluxed for from 10 to 30 hours and the product dimethyl compound (V, R 6 =R 7 =CH 3 ) isolated using known techniques.
An alternate method for the preparation of those compounds where one of R 6 and R 7 is hydrogen is available where one of R 6 and R 7 is benzyl. ##STR9##
The benzyl group is removed by treating compound V (R 7 =benzyl) with hydrogen generally under pressure of up to about 50 pounds per square inch (although atmospheric hydrogenation is also successful) in the presence of a catalyst such as palladium adsorbed on carbon. The reaction is preferably carried out in a polar solvent such as a lower alkanol. The choice of solvent is not critical so long as the solvent is stable under the reaction conditions employed. Generally the palladium is present on the carbon substrate to the extent of about 5%. The reaction is carried out generally at room temperature although heating to 50° C. is possible. The reaction is complete when a calculated molar equivalent of hydrogen has been reacted as observed by a decrease in the pressure or volume of the hydrogenation apparatus. It is also preferred if the starting material is utilized in the form of the hydrohalic acid addition salt.
The quaternary ammonium salts which form part of this invention are prepared from the compounds of structure V by treatment with a loweralkyl halide. ##STR10## Wherein R 8 is loweralkyl and Hal is a halide. The reaction is carried generally in a solvent such as a loweralkanol, preferably ethanol. The reaction mixture is generally stirred at room temperature, higher temperatures are generally not needed, and is complete in about 5 minutes to 1 hour. The product XII is isolated using known techniques.
The compounds of the present invention in the described dosages may be administered orally, however, other routes such as intraperitoneal, subcutaneous, intramuscular or intravenous may be employed.
The active compounds of the present invention are orally administered, for example, with an inert diluent or with an assimilable edible carrier, or they may be enclosed in hard or soft gelatin capsules, or they may be compressed into tablets, or they may be incorporated directly with the food of the diet. For oral therapeutic administration, the active compounds of this invention may be incorporated with excipients and used in the form of tablets, troches, capsules, elixirs, suppositories, suspensions, syrups, wafers, chewing gum, and the like. The amount of active compound in such therapeutically useful compositions or preparations is such that a suitable dosage will be obtained.
The tablets, troches, pills, capsules and the like may also contain the following: a binder such as gum tragacanth, acacia, corn starch or gelatin; an excipient such as diacalcium phosphate; a disintegrating agent such as corn starch, potato starch, alginic acid and the like; a lubricant such as magnesium stearate; and a sweetening agent such as sucrose, lactose or saccharin may be added or a flavoring agent such as peppermint, oil of wintergreen, or cherry flavoring. When the dosage unit form is a capsule, it may contain in addition to materials of the above type, a liquid carrier such as a fatty oil. Various other materials may be present as coatings or to otherwise modify the physical form of the dosage unit, for instance, tablets, pills or capsules may be coated with shellac, sugar or both. A syrup or elixir may contain the active compounds, sucrose as a sweetening agent, methyl and propyl parabens as preservatives, a dye and a flavoring such as cherry or orange flavor. Of course, any material used in preparing any dosage unit form should be pharmaceutically pure and substantially non-toxic in the amounts employed.
EXAMPLE 1
2-Amino-5,7-diethyl-1,8-naphthyridine
To 50 ml. of 85% phosphoric acid is added with stirring 2,6-diaminopyridine (6.55 g., 0.06 mole) followed by 3,5-heptanedione (7.7 g., 0.06 mole). The mixture is heated on the steam bath under nitrogen atmosphere for 16 hours. The reaction mixture is poured into crushed ice and neutralized with concentrated ammonium hydroxide and extracted with methylene chloride (3×250 ml.). The combined extracts are dried, filtered and concentrated in vacuo. Crystallization of the residue from ethyl acetate affords 2-amino-5,7-diethyl-1,8-naphthyridine melting at 187°-189° C.
EXAMPLE 2
The procedure of Example 1 is followed, using the compounds and reagents listed below to prepare the named naphthyridine compound:
______________________________________A. Phosphoric acid (85%) 100 ml. 2,6-Diaminopyridine 21.8 g. (0.20 mole) 1,1-Dimethoxy-5-methyl-3-hexanone 38.4 g. (0.20 mole)______________________________________
Affording 2-amino-7-isobutyl-1,8-naphthyridine m.p. 125°-127° C.
______________________________________B. Phosphoric acid (85%) 75 ml. 2,6-Diaminopyridine 16.35 g. (0.15 mole) 1,1-Dimethoxy-3-oxyopentane 21.9 g. (0.15 mole)______________________________________
Affording 2-amino-7-ethyl-1,8-naphthyridine m.p. 169.5°-172.5° C.
______________________________________C. Phosphoric acid (85%) 50 ml. 2,6-Diaminopyridine 15.0 g. (0.137 mole) 1,1-Dimethoxy-4-methyl-3-pentanone 19.5 g. (0.122 mole)______________________________________
Affording 2-amino 7-isopropyl-1,8-naphthyridine m.p. 158°-160.5° C.
______________________________________D. Phosphoric acid (85%) 50 ml. 2,6-Diaminopyridine 10.9 g. (0.10 mole) 3-methylpentan-2,4-dione 11.4 g. (0.10 mole)______________________________________
Affording 2-amino-5,6,7-trimethyl-1,8-naphthyridine as a brown solid.
______________________________________E. Phosphoric acid (85%) 100 ml. 2,6-Diamino-3-phenyl pyridine 10.7 g. (0.06 mole) 2,4-pentandione 6.0 g. (0.06 mole)______________________________________
Affording 2-amino-3-phenyl-5,7-dimethyl-1,8-naphthyridine m.p. 191°-195° C.
______________________________________F. Phosphoric acid (85%) 100 ml. 1,3-Diaminoisoquinoline 10.0 g. (0.063 mole) 2,4-Pentanedione 6.5 g. (0.066 mole)______________________________________
Affording 6-amino-1,1-dimethylbenzo[c][1,8]naphthylridine m.p. 253°-260° C.
EXAMPLE 3
2-Amino-5-methyl-7-methoxy-1,8-naphthyridine
To a suspension of 2-acetamido-5-methyl-7-chloro-1,8-naphthyridine (23.5 g., 0.10 mole) in 250 ml. of methanol is added sodium methoxide (16.2 g., 0.30 mole). The resulting solution is stirred at reflux under nitrogen atmosphere for 18 hours. The methanol is removed in vacuo and the residue is taken up in chloroform (250 ml.) and water (100 ml.). The chloroform layer is separated, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue is recrystallized from ethanol to yield 2-amino-5-methyl-7-methoxy-1,8-naphthyridine melting at 233°-236° C.
EXAMPLE 4
5,7-Diethyl-1,8-naphthyridin-2(1H)-one
To a stirred solution of 2-amino-,5,7-diethyl-1,8-naphthyridine (7.0 g., 0.035 mole) in 45 ml. of trifluoroacetic acid is added sodium nitrite (2.66 g., 0.0385 mole) in small portions over 1 hour at -5° C. The mixture is stirred at -5° C. for 2 hours and for an additional hour at room temperature. The reaction mixture is poured into 300 g. of crushed ice and is made alkaline with a slight excess of concentrated ammonium hydroxide. A yellow solid separates and is filtered and washed with a little ice water. Recrystallization from ethyl acetate affords 5,7-diethyl-1,8-naphthyridin-2-(1H)-one melting at 159°-161° C.
EXAMPLE 5
The procedure of Example 4 is followed, using the compounds and reagents listed below to prepare the named naphthyridine-2-(1H)-one compound.
______________________________________A. Trifluoroacetic acid 100 ml. Sodium nitrite 8.3 g. (0.12 mole) 2-Amino-7-isobutyl-1,8-naphthyridine 20.1 g. (0.10 mole)______________________________________
Affording 7-isobutyl-1,8-naphthyridine-2(1H)-one m.p. 135°-137° C.
______________________________________B. Triflouroacetic acid 30 ml. Sodium nitrite 6.55 g. (0.095 mole) 2-Amino-7-ethyl-1,8-naphthyridine 13.85 g. (0.08 mole)______________________________________
Affording 7-ethyl-1,8-naphthyridine-2(1H)-one m.p. 133°-134.5° C.
______________________________________C. Trifluoroacetic acid 30 ml. Sodium nitrite 5.52 g. (0.08 mole) 2-Amino-7-isopropyl-1,8- naphthyridine 7.5 g. (0.04 mole)______________________________________
Affording 7-isopropyl-1,8-naphthyridine-2(1H)-one
______________________________________D. Trifluoroacetic acid 50 ml. Sodium nitrite 6.9 g. (0.10 mole) 2-Amino-5,6,7-trimethyl-1,8- naphthyridine 10.0 g. (0.0535 mole)______________________________________
Affording 5,6,7-trimethyl-1,8-naphthyridine 2(1H)-one m.p. 170°-175° C.
______________________________________E. Trifluoroacetic acid 45 ml. Sodium nitrite 5.3 g. (0.77 mole) 2-Amino-3-phenyl-5,7-dimethyl-1,8- naphthyridine 8.6 g. (0.035 mole)______________________________________
Affording 3-phenyl-5,7-dimethyl-1,8-naphthyridine-2(1H)-one m.p. 258°-260° C.
______________________________________F. Trifluoroacetic acid 45 ml. Sodium nitrite 6.9 g. (0.1 mole) 6-Amino-1,3-dimethylbenzo[c] [1.8] naphthyridine 10.0 g. (0.045 mole)______________________________________
Affording 1,3-dimethylbenzo[c][1,8]naphthylridine-6(5H)-one m.p. 276°-278° C.
______________________________________G. Trifluoroacetic acid 60 ml. Sodium nitrite 11.0 g. (0.16 mole) 2-Amino-5-methyl-7-methoxy-1,8- naphthyridine 15.1 g. (0.08 mole)______________________________________
Affording 5-methyl-7-methoxy-1,8-naphthyridine-2(1H)-one m.p. 214°-216.5° C.
EXAMPLE 6
1-(2-Dimethylaminoethyl)-5,7-diethyl-1,8-naphthyridin-2(1H)-one
To a suspension of 5,7-diethyl-1,8-naphthyridin-2(1H)-one (4.04 g., 0.02 mole) in 25 ml. of dry dimethylformamide under nitrogen atmosphere is added a 57% suspension of sodium hydride in mineral oil (0.84 g., 0.02 mole). This mixture is stirred at room temperature for 0.5 hours. Then a mixture of 2-dimethylaminoethyl chloride hydrochloride (3.17 g., 0.022 mole) and a 57% suspension of sodium hydride in mineral oil (0.93 g., 0.022 mole) in 25 ml. of dry dimethylformamide is added to the above suspension. The mixture is stirred at steam bath temperature overnight (16 hours). After the mixture is cooled to room temperature it is filtered to remove salt (2.6 g., theory 2.45 g.). Removal of the solvent under reduced pressure gives a pale tan waxy solid (4.8 g.). Several recrystallizations from hexane gives 1-(2-dimethylaminoethyl)-5,7-diethyl-1,8-naphthyridin-2(1H)-one melting at 59.5°-61° C.
EXAMPLE 7
The procedure of Example 6 is followed to prepare other 1-substituted naphthyridine-2(1H)-ones according to the following reaction scheme: ##STR11## The substituent groups and the quantities of each reagent and compound employed are set forth in Table I.
In Table I, where the product is indicated as being isolated as a salt, such salt is prepared by adding to a solution of the free base in a suitable solvent, such as an alcohol, a solution of the desired acid in a similar solvent.
TABLE I__________________________________________________________________________ D A B C Melting PointR.sub.1R.sub.2 R.sub.3 R.sub.4 R.sub.5 g.(moles) g. (moles) g. (moles) (salt)__________________________________________________________________________a H H H H isobutyl 12.1 (0.06) 9.36 (0.065) 5.27 (0.125) 189°-191° C. (HCl)b H H H H CH.sub.3 4.8 (0.03) 4.75 (0.033) 2.65 (0.063) 200°-203.5° C. (HCl) . H.sub.2 Oc H H H H C.sub.2 H.sub.5 10.4 (0.06) 10.16 (0.07) 5.46 (0.13) 146°-149° C. (HCl) 1/22H.sub.2 Od H H H CH.sub.3 H 1.6 (0.01) 1.58 (0.011) 0.88 (0.021) 207°-210° C. (HCl)e H H CH.sub.3 H H 4.0 (0.025) 4.32 (0.03) 2.3 (0.055) 228°-230° C. (HCl)f H H CF.sub.3 H CF.sub.3 5.64 (0.02) 3.6 (0.025) 1.89 (0.045) 203.5°-206.5.degre e. C. (HCl) . H.sub.2 Og H H CF.sub.3 H CH.sub.3 0.55 (0.0024) 0.43 (0.003) 0.226 (0.0054) 102.5°-103.5.degre e. C. 1/2 H.sub.2 Oh H H CH.sub.3 H CF.sub.3 1.0 (0.0044) 0.72 (0.005) 0.395 (0.0094) 86°-87.5° C.i H CH.sub.3 H H NH.sub.2 14.0 (0.08) 11.5 (0.08) 6.74 (0.16) 168°-172° C.j H H H H NH.sub.2 12.9 (0.08) 11.5 (0.08) 6.74 (0.16) 134.5°-137° C.k H H H H CH(CH.sub.3).sub.2 9.4 (0.05) 7.92 (0.055) 4.42 (0.105) 207°-210.5° C. (HCl)l H H CH.sub.3 CH.sub.3 CH.sub.3 5.3 (0.028) 4.04 (0.028) 2.36 (0.056) 180°-185° C. (HCl) . H.sub.2 Om H H CH.sub.3 H --OCH.sub.3 11.4 (0.06) 8.65 (0.06) 5.06 (0.12) 98.5°-101.5.degree . C.n H H H H H 2% (0.02) 2.9 (0.02) 1.7 (0.041) 202°-203° C. (HCl)__________________________________________________________________________
EXAMPLE 8
A. 1-(2-Diethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one Hydrochloride
5,7-Dimethyl-1,8-naphthyridin-1,8-naphthyridin-2(1H)-one(3.48 g., 0.02 mole) is added to a solution of sodium ethoxide made by disolving sodium pellets (1.0 g., 0.043 mole) in 50 ml. of ethanol. The mixture is heated to reflux and a solution of 2-diethylaminoethyl chloride hydrochloride (3.44 g., 0.02 mole) in 50 ml. of absolute ethanol is added in a dropwise manner. Heating under reflux is continued for six hours, the mixture is cooled, filtered and evaporated under reduced pressure. The residue is dissolved in ether and extracted with dilute hydrochloric acid. The acidic extract is filtered through charcoal and made basic with saturated sodium carbonate solution. The product is extracted into ether, containing the free base of the title compound, is dried with anhydrous sodium sulfate and the hydrochloride salt is prepared by addition of ethereal hydrogen chloride. The salt is collected and recrystallized from isopropanol to yield 3.56 g. of 1-(2-diethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one hydrochloride with a m.p. of 226°-228° C.
B. 1-(2-Dimehylaminoethyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-one
Following the above procedure employing dimethylamino ethyl chloride hydrochloride as the alkylating reagent, there is obtained 1-(2-dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-one.
EXAMPLE 9
The procedure of Example 8 is followed to prepare the 1-substituted naphthyridin-2(1H)-ones according to the following reaction scheme: ##STR12##
The substituent groups and the quantities of each reagent and compound employed are set forth in Table II.
In parts (d) and (h) of Table II the "pyrrolidinyl" and "2,2,6,6-tetramethylpiperidins" designations for R 6 and R 7 indicate that the named groups include the nitrogen atoms to which R 6 and R 7 are attached.
In part e of Table II the value of "3" for n indicates a propylene group.
In part g of Table II the value of "4" for n indicates a "2-methylpropylene" group.
In parts g and h of Table II the acid addition salt is not prepared, thus the procedure of Example 8 describing the acidification of the ether solution is omitted.
TABLE II__________________________________________________________________________ H E F G(Na) Melting PointR.sub.6 R.sub.7 n g.(moles) g.(moles) g.(moles) (salt)__________________________________________________________________________a n-butyl n-butyl 2 2.6 (0.015) 3.4 (0.015) 0.75 (0.033) 195°-197° C. (HCl) . 1/2H.sub.2 Ob isopropyl isopropyl 2 3.5 (0.02) 4.0 (0.02) 1.0 (0.043) 261°-262° C. (HCl)c cyclohexyl cyclohexyl 2 2.6 (0.015) 4.2 (0.015) 0.75 (0.033) 259°-260° C. (HCl)d pyrrolidinyl 2 3.5 (0.02) 3.4 (0.02) 1.0 (0.043) 216°-217° C. (HCl)e methyl methyl 3 3.5 (0.02) 3.2 (0.02) 1.0 (0.043) 232°-234° C. (HCl)f benzyl methyl 2 15.7 (0.09) 19.8 (0.09) 4.5 (0.019) 208°-210° C. (HCl)g methyl methyl 4 10.8 (0.06) 12.9 (0.075) 3.4 (0.015) 109°-111° C.h 2,2,6,6-tetramethylpiperidino 2 2.6 (0.015) 3.6 (0.015) 0.75 (0.033) 170°-172°__________________________________________________________________________ C.
EXAMPLE 10
The procedure of Example 8 is followed using the compounds and reagents listed below in ethanol to prepare the named naphthyridin-one compounds:
______________________________________A. Sodium 1.34 g. (0.058 mole) Dimethylaminoethylchloride 4.15 g. (0.029 mole) hydrochloride 3-Phenyl-5,7-dimethyl-1,8- naphthyridin-2(1H)-one 6.0 g. (0.024 mole)______________________________________
Affording 1-(2-dimethylaminoethyl)-3-phenyl-5,7-dimethyl-1,8-naphthyridin-2(1H)-one m.p. 135°-137° C.
______________________________________B. Sodium 1.34 g. (0.058 mole) Dimethylaminoethylchloride hydrochloride 4.15 g. (0.029 mole) 1,3-Dimethylbenzo[c][1,8] naphthyridin-6(5H)-one 5.38 g. (0.024 mole)______________________________________
Affording 5-dimethylaminoethyl-1,3-dimethylbenzo[c][1,8]naphthyridin-6[5H]-one m.p. 128.5°-130.5° C.
EXAMPLE 11
A. 1-(2-Phthalimidoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one
To a suspension of 5,7-dimethyl-1,8-naphthyridin-2(1H)-one (3.5 g., 0.02 mole) in 25 ml. of dry dimethyl formamide under nitrogen atmosphere is added a 57% suspension of sodium hydride in mineral oil (0.84 g., 0.02 mole). This mixture is stirred at room temperature for 1/2 hour. A mixture of N-(2-chloroethyl) phthalimide (4.6 g., 0.022 mole) in 25 ml. of dry dimethylformamide is added to the first suspension. The mixture is stirred at steam bath temperature for 16 hours. On cooling, it is filtered to remove salt and the filtrate evaporated to dryness in vacuo to afford 1-(2-phthalimidoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one.
B. 1(4-Phthalimidobutyl)-5,7-dimethyl-1,8-naphthyridin-2-(1H)-one
The above procedure is employed with equimolar quantities of N-(4-chlorobutyl) phthalimide, to prepare 1(4-phthalimidobutyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one.
EXAMPLE 12
A. 1-(2-Aminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one Hydrochloride
A mixture of 1-(2-phthalimidoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one (5.2 gm., 0.015 mole) and 95% hydrazine (1.8 ml., 0.053 mole) in absolute ethanol (50 ml.) is refluxed for one hour. The reaction is cooled, water (37.8 ml.) and concentrated hydrochloric acid (37.5 ml.) are added. After refluxing for one half hour, the mixture is cooled in an ice bath and phthalhydrazide (2.85 gm., 0.0125 mole) is filtered off. The filtrate is concentrated and the residue is dissolved in water, made basic with saturated sodium carbonate and extracted with methylene chloride. The organic layer is dried over anhydrous sodium sulfate, filtered and evaporated. The residue containing the free base of the title compound is dissolved in a minimum amount of methanol and treated with ethereal hydrogen chloride. Recrystallization of the product from isopropanol gives 1-(2-aminoethyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-one hydrochloride melting at 253.5°-254.5° C.
B. 1-(4-Aminobutyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-Hydrochloride
The above procedure is employed with equimolar quantities of 1-(4-phthalimidobutyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-one to prepare 1-(4-aminobutyl)-5,7-dimethyl-1,8-naphthyridine-2(1H)-one hydrochloride m.p. 188°-190° C. or the free base of such compound.
EXAMPLE 13
A. 1-{2-[(N-methylthiocarbamoyl)amino]ethyl}-5,7-dimethyl-1,8-naphthyridin-2(1H)-one
A mixture of the free base of 1-(2-aminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one (700 mg., 0.0032 mole) as prepared in Example 12 and methyl isothiocyanate (180 mg., 0.004 mole) in 5 ml. of water is heated at reflux for 30 minutes. On cooling the reaction, the product is collected by filtration. After recrystallization from methanol, 1-{2-[(N-methylthiocarbamoyl)amino]ethyl}-5,7-dimethyl-1,8-naphthyridin-2(1H)-one m.p. 216.5°-218° C. is obtained.
B. 1-{4-[(N-methylthiocarbamoyl)amino]butyl}-5,7-dimethyl-1,8-naphthyridine-2(1H)-one
The above procedure is employed with equimolar quantities of 1-(4-aminobutyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one to prepare 1-{4-[(N-methylthiocarbamoyl)amino]butyl}-5,7-dimethyl-1,8-naphthyridin-2(1H)-one m.p. 147°-149° C.
EXAMPLE 14
1-(2-Methylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one Hydrochloride
1(2-Benzylmethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one hydrochloride (8.56 g., 0.024 mole) is dissolved in 80 ml. of ethanol, 5% palladium on carbon (0.8 g.) catalyst is added and the mixture is hydrogenated at a pressure of 45 lbs. per sq. inch until hydrogen is no longer taken up. The mixture is filtered concentrated under reduced pressure and the residue is crystallized from isopropanol. 1-(2-Methylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one hydrochloride having a melting point of 106°-109° C. is obtained.
EXAMPLE 15
1-(4-Dimethylaminobutyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one Dihydrobromide
Formic acid (10 ml., 0.265 mole) is added with stirring at 5° C. in 1 ml. portions to 1-(4-aminobutyl)-5,7-dimethyl-1,8-naphthyridin-2-(1H)-one (13.7 g., 0.056 mole) (obtained as the free base from Example 12B). Formaldehyde (37%, 10 ml.) is added to the semi-solid mass and the mixture is refluxed for 18 hours. On cooling, hydrochloric acid (12 N, 13.7 ml.) is added and the mixture concentrated under vacuum. The residue is dissolved in water and the solution is made alkaline with excess sodium hydroxide. The product is extracted into diethyl ether. The ethereal solution is dried over sodium sulfate and filtered. Aqueous hydrobromic acid is added to the filtrate and the mixture concentrated under vacuum. The residue is recrystallized from ethanolethyl ether to yield 1-(4-dimethylaminobutyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one dihydrobromide melting at 222°-225° C.
EXAMPLE 16
N-{[1,2-Dihydro-2-oxo-5,7-dimethyl-1-(1,8-naphthyridyl)]ethyl}-N,N,N-trimethylammonium Iodide
Methyl iodide (1,7 g., 0.012 mole) is added to a solution of 1-(2-dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one (2.45 g., 0.01 mole) (obtained as the free base from Example 8B) in 10 ml. of absolute ethanol and the mixture is stirred for 20 minutes. Ethyl ether is added and the precipitated product is filtered and recrystallized from methanol/ethyl ether to give N-{[1,2-dihydro-2-oxo-5,7-dimethyl-1-(1,8-naphthyridyl)]ethyl}-N,N,N-trimethylammonium iodide with a melting point of 219°-220° C.
EXAMPLE 17
1-(2-Dimethylaminoethyl)-5,7-dimethyl-3,4-dihydro-1,8-naphthyridin-2(1H)-one Dihydrobromide
A solution of 1-(2-dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one hydrochloride (2.82 g., 0.01 mole) in 35 ml. of glacial acetic acid containing 300 mg. of platinum oxide is hydrogenated at atmospheric pressure until 0.01 mole of hydrogen is taken up. The mixture is filtered, the solvent is evaporated and the residue is dissolved in water. After filtration through charcoal, the solution is made basic with sodium carbonate, and the free base of the title product is extracted with ethyl ether. An ethereal solution of hydrogen bromide is added and the precipitate is recrystallized from methanolethyl ether to yield 1-(2-dimethylaminoethyl)-5,7-dimethyl-3,4-dihydro-1,8-naphthyridin-2(1H)-one dihydrobromide with a melting point of 218°-221° C.
EXAMPLE 18
The procedure of Example 17 may be employed to reduce other naphthyridin-2(1H)-ones to the corresponding 3,4-dihydronaphthyridin-2(1H)-ones. By following said hydrogenation procedure the products listed below are obtained:
A. 1-(2-Dimethylaminoethyl)-7-ethyl-3,4-dihydro-1,8-naphthyridin-2(1H)-one hydrochloride
B. 1-(4-Dimethylaminobutyl)-5,7-dimethyl-3,4-dihydro-1,8-naphthyridin-2(1H)-one
C. 1-(2-Aminoethyl)-5,7-dimethyl-3,4-dihydro-1,8-naphthyridin-2(1H)-one hydrobromide
D. 1-(2-Dimethylaminoethyl)-5-methyl-7-methoxy-3,4-dihydro-1,8-naphthyridin-2(1H)-one
E. 1-(2-Methylaminoethyl)-5,7-dimethyl-3,4-dihydro-1,8-naphthyridine-2(1H)-one hydrochloride.
F. 1-(2-Dimethylaminoethyl)-7-amino-3,4-dihydro-1,8-naphthyridin-2(1H)-one dihydrochloride.
The compounds prepared by this procedure may be isolated as the free base, such as compound B or as the acid addition salt which are prepared by the procedure described in Example 17.
EXAMPLE 19
1-(2-Dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-thione Hydrochloride
A mixture of 1-(2-dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-one (2.5 g., 0.01 mole) and phosphorus pentasulfide (2.0 g., 0.009 mole) in 60 ml. of methylene chloride is heated at reflux for 4 hours. The reaction is cooled, water and solid potassium carbonate added, and the organic layer is separated, dried, filtered through charcoal and evaporated to dryness. The residue is dissolved in ether, hydrogen chloride is added and the salt is recrystallized from isopropanol to yield 1-(2-dimethylaminoethyl)-5,7-dimethyl-1,8-naphthyridin-2(1H)-thione hydrochloride m.p. 209°-211° C.
EXAMPLE 20
The procedure of Example 19 is followed to prepare other naphthyridin-2(1H) thiones according to the following reaction scheme: ##STR13##
In item g of Table III the value of 4 for n indicates the 2-methylpropylene group.
TABLE III______________________________________R.sub.1 R.sub.3 R.sub.4 R.sub.5 R.sub.6 R.sub.7 n______________________________________a H H H CH.sub.3 CH.sub.3 CH.sub.3 2b H CH.sub.3 H H CH.sub.3 CH.sub.3 2c H C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 2d C.sub.6 H.sub.5 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 2e H CH.sub.3 H CH.sub.3 CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2 2f H CH.sub.3 H CH.sub.3 --(CH.sub.2).sub.4 2g H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 4h H H CH.sub.3 H CH.sub.3 CH.sub.3 2______________________________________
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Organic chemical compounds based upon the naphthyridine molecule are disclosed which have potent gastric secretion inhibitory properties. The naphthyridinone is substituted with a substituted amino alkyl group at the 1-position, and variously substituted at the remaining positions. The compounds have profound effects on the inhibition of gastric secretions in the gastro-intestinal tract, and compositions for such uses are also disclosed.
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BACKGROUND
[0001] While drilling and producing wells for the recovery of petroleum and other subsurface deposits, it is often necessary to close off or plug a tubular conduit, such as a string of tubing extending from the well surface to a subterranean location, at a chosen point along the length of the conduit. Subsequently, it is necessary to be able to re-open the conduit for flow therethrough. A plug used to close off the tubing during setting of a well tool, such as a packer, may then be released so that fluid may be circulated through the tubing.
[0002] Certain types of plugs are designed to be permanently installed, and they must be drilled or milled to be removed, which can be labor intensive. Other types of plugs are designed to be retrieved when the purpose for which the plug has been installed has been accomplished. Retrievable plugs generally employ some form of releasable anchoring device by which the plug may be secured to the internal bore of the well pipe and which may then be released to enable the plug to be withdrawn. One disadvantage of this prior art arrangement is that a restriction in the internal diameter of the tubing string often accompanies the design. Also, the prior art plugs were often retrieved on a wireline and the retrieval operation was complicated in the case of deviated well bores. Debris that sometimes accumulates on the top of the retrievable plug can also cause issues in the wellbore.
[0003] Another prior art plug design involves the incorporation of a plug of expendable material and an actuating device used to dislocate or fracture the plug upon receipt of a triggering signal. The potential for remaining and problematic debris from the plug in the tubing string or wellbore must be carefully monitored in such devices. Sand plugs, for instance, have been provided for zonal isolation within wellbores, however the integrity of such sand plugs can be inconsistent and remaining particulates must be dealt with.
BRIEF DESCRIPTION
[0004] A plug disposable in a well bore to block fluid from passing through the wellbore, the plug includes a body formed from water soluble glass, the body dissolvable in water.
[0005] An apparatus which controls flow of well bore fluids from a production zone located within a subterranean formation adjacent the well bore to a well surface, the apparatus includes a tubular housing extending from the well surface to a selected depth within the well bore, the tubular housing having an internal bore for passage of fluids; and, a plug including a body formed from water soluble glass, the body dissolvable in water, the plug positioned within the tubular housing to initially close off the internal bore of the housing.
[0006] A method of utilizing water soluble glass in a downhole fluid conducting system, the method includes employing an element formed of water soluble glass; performing a first function in the system when the element is present; dissolving the element in the presence of water; and performing a second function in the system different than the first function.
[0007] A system which detects presence of formation water in an underground location, the system includes a casing insertable within a wellbore; a chemical sensor within the casing; and a first water detection body including a first detectable chemical element surrounded by water soluble glass, wherein the first water detection body is locatable within a fractured formation and the chemical sensor senses the first detectable chemical element when formation water dissolves the water soluble glass
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
[0009] FIG. 1 depicts a schematic view of a well bore completion showing an exemplary embodiment of a dissolvable plug;
[0010] FIG. 2 depicts a cross sectional view of an exemplary embodiment of the dissolvable plug of FIG. 1 ;
[0011] FIG. 3 depicts a cross sectional view of another exemplary embodiment of the dissolvable plug of FIG. 1 ;
[0012] FIG. 4 depicts a cross-sectional view of an exemplary embodiment of a dissolution advancement system;
[0013] FIGS. 5A-5C depict various embodiments of a protective oil-based layer on the dissolvable plug of FIG. 1 ;
[0014] FIG. 6 depicts a schematic view of an exemplary embodiment of a chemical employing system for removing the protective oil-based layer of FIGS. 5A-5C ;
[0015] FIG. 7 depicts a schematic view of an exemplary embodiment of a mechanical device for removing the protective oil-based layer of FIGS. 5A-5C ;
[0016] FIG. 8 depicts a schematic view of an exemplary embodiment of a system for detecting formation water;
[0017] FIG. 9 depicts a circuit diagram for use with a chemical sensor within the exemplary system of FIG. 8 ; and,
[0018] FIG. 10 depicts a circuit diagram of an exemplary embodiment of a closure device.
DETAILED DESCRIPTION
[0019] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0020] Referring to FIG. 1 , a wellbore 10 is shown lined with a casing 12 , also known as a tubular, tubular housing, string, etc. A tubing mounted valve 14 may be located within the string of casing 12 . A packer 16 isolates an annular region 18 between the casing 12 and the wellbore 10 . According to exemplary embodiments of the present invention, a dissolvable plug 20 initially closes off flow from a perforated zone 100 up the internal bore 22 of the casing 12 to the well surface 24 . The dissolvable plug 20 forms a portion of the well tool 26 , and may, in one exemplary embodiment, have an outer diameter which is approximately equal to an internal diameter of the casing 12 forming the flow path to the well surface 24 where the plug 20 is seated. Thus, the plug 20 advantageously need not require any significant constructions or devices that restricts an internal diameter of the internal bore 22 of the casing 12 , however, as shown in FIG. 2 , a small seat 30 such as seating device or shoulder or other protrusion may be provided to ensure that the plug 20 does not slide out of place. In an exemplary embodiment, the seating device 30 may be made from the same dissolvable material as the plug 20 .
[0021] In an alternative exemplary embodiment shown in FIG. 3 , in lieu of seating device 30 , the casing 12 may include a section 36 have an internal diameter in an area for receiving the plug 20 that is larger than an internal diameter of a remainder of the internal bore 22 of the casing 12 . In this case, the plug 20 may be formed with the casing 12 prior to positioning the tubing in the wellbore 10 .
[0022] The plug 20 may be formed and pre stressed within a section of the tubing string or casing 12 to provide sufficient strength against pressure within the tubing. In an alternative exemplary embodiment, the plug 20 may first be formed as a separate element and then secured within the casing 12 using an adhesive component such as, but not limited to, the same dissolvable material as the plug 20 .
[0023] In these exemplary embodiments, the plug 20 is made of water soluble glass, which is made from silica and soda. Soda reduces the melting point of silica, which makes it easier to create glass, and soda also renders the glass water soluble. The most prevalent type of glass is soda-lime glass, also called soda-lime-silica glass, where the lime is added to restore insolubility. In one exemplary embodiment of the plug 20 , made from soda and silica and without lime, the water soluble glass plug 20 will dissolve when in contact with water or steam. Some samples have been shown to dissolve at a rate of about 0.0001″ per minute at about 180° F., however the solubility rate is temperature sensitive to the water that it is dissolved in, and salt water has been shown to dissolve the water soluble glass at a slower rate. In a non aqueous environment, the material remains intact at high temperatures, such as about 1500° F. to about 2000° F. As another important feature, the plug 20 is insoluble to oil and petroleum based liquids and this feature may be advantageously employed in the present invention.
[0024] In one exemplary embodiment, the plug 20 is formed using water soluble glass with dimensions and content suitable for its intended applications. By varying and balancing both the thickness of the plug and the content of soda in the glass matrix, the solubility can be modulated. For example, the thickness and soda content of a plug 20 can be adjusted such that a wellbore tool 26 , such as a packer, remains plugged until the required operation is carried out.
[0025] While the plug 20 may be installed in the casing 12 using conventional methods, the removal of the plug 20 may be determined based on intended use. In one exemplary embodiment, the plug 20 is installed in the wellbore tool 26 in a conventional manner and may be allowed to begin dissolving while the operation is being carried out, so long as the plug 20 is not completely dissolved until after the operation is completed. In another exemplary embodiment, the thickness of the plug 20 may be sufficiently thick and the soda content sufficiently low such that the plug 20 barely dissolves even in the presence of water to guarantee that a required operation is completed before dissolution.
[0026] In an exemplary embodiment shown in FIG. 4 , to advance the dissolution of the plug 20 , at least one fluid port 40 , or a plurality of fluid ports 40 may be provided in an area circumferentially surrounding the plug 20 . Water or heated water may be provided to the plug 20 at a time when the plug 20 is to be dissolved. The temperature of the water and the time the plug 20 is exposed to the water may both be selected to dissolve the plug 20 in a desired amount of time. The fluid ports 40 may be arranged such that the water or heated water is directed towards a portion of the plug 20 that is desired to be dissolved first.
[0027] In yet another exemplary embodiment, as shown in FIGS. 5A-5C , the plug 20 includes a protective oil-based layer 50 deployed on at least one surface of the plug 20 to prevent the plug 20 from coming into contact with water, thereby retaining its initial structure until the layer 50 is removed and water is introduced to the plug 20 . In an exemplary embodiment shown in FIG. 5A , the layer 50 is deployed on an upper surface 52 of the plug 20 , such as a surface facing an uphole direction of the wellbore 10 . In another exemplary embodiment shown in FIG. 5B , the lower surface 54 of the plug 20 includes a protective oil-based layer 50 , such as a surface facing a downhole direction of the wellbore 10 , and in yet another exemplary embodiment shown in FIG. 5C , at least both the upper and lower surfaces 52 , 54 of the plug 20 include a protective oil-based layer 50 , such as all surfaces of the plug 20 .
[0028] Removal of the oil-based layer 50 may be accomplished using a mechanical device and/or chemical means. To chemically remove the oil-based layer 50 , surfactants, such as emulsifiers, detergents, etc., may be used to break the bonds holding the molecules of the oil together so that the oil molecules can be separated and rinsed away. As shown in FIG. 6 , the chemical introduction may occur using fluid ports 40 that direct the oil removing chemical substance towards the oil-based layer 50 . These may be the same ports 40 that direct water or heated water to the plug 20 for dissolution of the plug 20 . The fluid ports 40 may also be used to vacuum the oil removing chemical substance and oil-based layer 50 away from the plug 20 . While certain chemical removal embodiments are described, other devices to chemically remove the layer from the plug would be within the scope of these embodiments.
[0029] As shown in FIG. 7 , to mechanically remove the oil based layer 50 from the plug 20 , a mechanical device 56 may extend from the casing 12 , such as a scraper or brush which may be used to at least partially remove the protective layer. The scraper or brush may be a single blade used to wipe off the oil, matter used to absorb the oil, a series of bristles, etc. The mechanical device 56 may be actuated using known downhole tool actuators and may rotate along an interior of the casing 12 to wipe off the layer 56 . The mechanical device may also includes elements made of water soluble material, such as water soluble glass, such that it can also be dissolved in the presence of water. While certain mechanical removal embodiments are described, other devices to mechanically remove the layer from the plug would be within the scope of these embodiments.
[0030] Although the plug 20 has been described as being removed by dissolving with water, in yet another exemplary embodiment, the plug may be removed by first breaking the glass structure of the plug 20 . Breaking the glass structure of the plug 20 may be accomplished by using any known fracturing technique. By fracturing the plug 20 and introducing water to interior surfaces of the plug 20 , the plug 20 will quickly dissolve and be absorbed by the wellbore fluid.
[0031] The exemplary embodiments disclosed thus far have provided a glass water soluble plug 20 for use in plugging a tool 26 until removal of the plug 20 is warranted. Alternative exemplary embodiments of designs and methods for employing the water soluble glass material within the wellbore 10 will now be described.
[0032] In one exemplary embodiment for employing water soluble glass in a wellbore 10 , as shown in FIG. 8 , the water soluble glass is used as a carrier for long term curing chemicals, which are embedded in the glass matrix, for fracturing/stimulating operations. The glass body 104 , when sent down the well bore 10 or into perforations 100 would be able to store chemicals underground and release them only when exposed to formation water. When the glass body 104 is dissolved by formation water, the chemicals are released and enter the casing 12 through openings 108 in tool 110 and they may then be sensed by a chemical sensor 106 , which in turn may send a communication signal that indicates the presence of formation water, may actuate a downhole tool such as opening or closing a sleeve, or may increase a count on a counter.
[0033] Similar to the above-described exemplary embodiment, in another exemplary embodiment for employing water soluble glass in a wellbore 10 , different detectable chemical elements are embedded in the glass matrix and glass bodies 112 including the different detectable chemical elements are pumped in multi-layered fractured formations. That is, a glass body or bodies 104 containing a first detectable chemical element may be pumped or otherwise directed into a first layer or perforation 100 of the well, while a glass body or bodies 112 containing a second detectable chemical element, different than the first detectable chemical element, is pumped into a second layer or perforation 102 of the well which is distanced from the first layer or perforation 100 . First and second chemical sensors 106 , 114 may be positioned within the casing 12 for detecting the existence of the corresponding chemicals, and may trigger the appropriate response as described above. While only two different detectable chemical elements and layers are described, it would be within the scope of these embodiments to include multiple different chemical elements for detecting formation water from any number of layers. Thus, it is possible to detect from what specific layer formation water is coming from depending on which chemical sensor is activated. While two chemical sensors have been described, it would also be within the scope of these embodiments to employ a single chemical sensor, which reacts differently, depending on which chemical is detected.
[0034] An exemplary embodiment of chemical sensor 106 is shown in FIG. 9 . Sensor 106 is communicatively connected to and triggers switch 116 closing a circuit to battery 118 and powering actuation mechanism 120 .
[0035] In yet another exemplary embodiment, the water soluble glass is used as an inexpensive override system to actuate a downhole tool. In one such exemplary embodiment, the water soluble glass may be used to shut down a non-deepset safety valve. In a condition where the chamber becomes flooded by water, replacing oil initially present, a passive dissolvable part made with the water soluble glass may then initiate a process that leads to the final closure of a flapper. The process may be completely mechanical, such as by the passive dissolvable part releasing a latch. Alternatively, as represented by FIG. 10 , the dissolvable part 122 may include an electrode and when a water soluble glass covering of the part 122 is dissolved by water, the electrode is ground to the casing 12 or to the wellbore fluids and completes the circuit. Dissolving the encapsulated electrode completes the circuit and allows power to flow across the actuator mechanism 126 to actuate the downhole tool.
[0036] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
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A plug disposable in a well bore to block fluid from passing through the wellbore. The plug includes a body formed from water soluble glass. The body dissolvable in water. A method of utilizing water soluble glass is included.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to mixtures of chromogens that are especially useful as color formers in carbonless copying systems.
2. Description of the Prior Art
Chromogenic mixtures that form "black" shades are highly desirable for use in pressure sensitive carbonless recording systems. "Black" images have superior reproduction characteristics when copied by xerographic processes. Additionally, "black" images provide excellent contrast, readability and are similar in appearance to traditional typewritten copy. In the context of carbonless systems, the term "black" refers to shades that range from dark gray to black in appearance and that are characterized by approximately straight line absorption throughout the entire visible range, approximately 400-700 millimicrons.
The traditional carbonless recording system includes a top sheet that is coated on its back surface ("CB") with a multitude of microcapsules containing a marking liquid and a bottom sheet coated on its front ("CF") with an acidic material, such as an acidic clay or a phenolic resin, that reacts with the normally colorless marking fluid upon rupture of the CB microcapsules to form an image on the CF. The marking fluid contained in the microcapsules coated on the CB is typically a mixture of chromogenic materials dissolved within a carrier oil or fluid.
Zinc-modified phenolic resins are now widely favored as the acidic material coated on the CF. This is due to their high reactivity, stabilizing effect on the formed images with respect to light and dark exposure and their low abrasiveness on paper coating equipment. However, zinc-modified phenolic resins display an unexpected inability to synergistically react with many mixtures of two or more chromogens. Rather, most blends of chromogens when imaged on zinc-modified phenolic resins show antagonism with respect to the imaging properties of each other resulting in undesirable shades, poor intensity, or both. This antagonism problem is particularly evident in chromogenic blends intended to form "black" images.
To date, the traditional solution to this problem has been the use of so-called "single component black" precursors. These chromogens are generally blackish green colored fluorans that are used alone or in combination with small amounts (5%-20% by weight) of toner chromogens in order to achieve a preferred "black" shade and to avoid the blending antagonism caused by zinc-modified phenolic resins. However, the use of "single component blacks" is undesirable from a commercial standpoint since they are generally quite expensive and must be applied in relatively large amounts. Thus, there is a need for a chromogenic mixture that will produce a "black" shaded image with zinc-modified phenolic resins while avoiding the antagonistic blending characteristics of such resins and at the same time eliminating or substantially reducing the amount of "single component black" chromogen used.
Most chromogenic mixtures include crystal violet lactone (3,3-bis(p-dimethylamino phenyl), 6-dimethyl amino phthalide) as one of the chromogenic components. For example, U.S. Pat. Nos. 4,376,150 (Morita et al.); 4,180,405 (Lawton); and 4,168,845 (Oeda et al.) all disclose chromogenic mixtures including, inter alia, CVL and a green chromogen. U.S. Pat. Nos. 4,363,664 (Delaney); 4,324,817 (Dahm et al.); 4,275,906 (Johnson et al.); 4,263,047 (Miyamoto et al.); 4,262,936 (Miyamoto); 4,197,346 (Stevens); 4,032,690 (Kohmura); 3,952,117 (Miyamoto); 3,940,275 (Brockett et al.); and 3,560,229 (Farnham et al.) all disclose chromogenic mixtures including, inter alia, CVL and various other fluoran homologs, isomers and analogs. These blends, however, suffer from antagonism problems when imaged on zinc-modified phenolic resins. In addition, the blends disclosed in the Brockett et al are blue, not black. U.S. Pat. Nos. 3,857,675 (Schwab et al.) and 3,849,164 (Schwab et al.) both teach blends of essentially green and red chromogens to produce a "black" shade that avoid the use of CVL entirely. See also U.S. Pat. No. 4,073,614 (Ozutsumi et al.).
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a mixture of chromogens capable of forming a "black" shade when reacted with a zinc-modified phenolic resin in a carbonless copy system.
It is a further object of the present invention to provide a substantially colorless marking liquid composition containing a mixture of chromogens dissolved in an organic oil that is capable of producing a "black" image when reacted with a zinc-modified phenolic resin in a carbonless copy system.
It is a specific object of the present invention to provide a chromogenic mixture that includes at least three components. The first chromogenic component is an orange chromogen having the following formula: ##STR1## where R1, R2, and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof. This orange chromogen should be present in the chromogenic mixture in an amount of approximately 10% to 60% by weight based on the total weight of the mixture. The second component of the inventive chromogenic mixture is a blue, indigo or violet chromogen that should be present in an amount of approximately 5% to 60% by weight. The third chromogenic component is a green or single component black chromogen that is present in the mixture in an amount of approximately 30% to 70% by weight.
Further objects and embodiments of the present invention will become clear in the following description of the preferred embodiments and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 displays the spectrophotometric analysis in the visible range of the preferred embodiment disclosed in Example 1; and
FIG. 2 displays the spectrophotometric analysis in the visible range of the preferred embodiment disclosed in Example 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The orange chromogens that may form the first component of the inventive chromogenic mixture, alone or in combination, all have the following formula: ##STR2## where R1, R2, and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof. A most preferred orange chromogen has R1 and R3 as methyl groups and R2 as hydrogen. Its technical name is 6'-diethyl amino, 1',3'-dimethyl fluoran. Another preferred orange chromogen has R1 as methyl and R2 and R3 as hydrogen. Its technical name is 6'-diethyl amino, 3'-methyl fluoran. A third preferred orange chromogen has R2 as a tert-butyl group and R1 and R3 as hydrogen. Its technical name is 2'-t-butyl, 6'-diethyl amino fluoran. The orange chromogen should be present in the chromogenic mixture in an amount from approximately 10% to 60% based on the total weight of the chromogenic mixture. Most preferably the orange chromogen may be present in an amount from 24% to 35% by weight.
With respect to the blue, indigo or violet chromogen, three preferred candidates, which may be used alone or in combination, are crystal violet lactone, 6-dimethylamino, bis(3-dimethylaminophenyl, 1,3, dimethylaminophenyl)phthalide and 1',3',6',8' tetra(dimethylaminophenyl)phthalide. Most preferably, crystal violet lactone is used as the blue, indigo or violet chromogen since it is highly reactive, widely available and relatively low in cost. The blue, indigo or violet chromogen should be present in an amount of approximately 5% to 60% based on a total weight of the chromogenic mixture. Most preferably, the blue, indigo or violet chromogen may be present in an amount of approximately 10% to 20% by weight.
With respect to the green or single component black chromogen that forms the third component of the inventive chromogenic mixture, there are four preferred compounds, which may be used alone or in combination. The first is a single component black chromogen, 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino)fluoran. The second is a green chromogen, 2'(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran. These two chromogens are the most preferred green or single component black chromogens.
The third preferred chromogen is a green chromogen, 2'-(bis-phenyl methylamino), 4'-methyl, 6'-diethylamino fluoran. The fourth chromogen is a single component black chromogen, 2'-phenylamino, 3'-methyl, 6'(N-methyl, N-cyclohexylamino)fluoran. The selected green or single component black chromogen may be present in the inventive chromogenic mixture in an amount of approximately 30% to 70% based on the total weight of the mixture. Most preferably, the selected green or single component black chromogen may be present in an amount from 45% to 60% by weight.
To form the inventive chromogenic mixtures, one or more of the chromogens from each of the three classes is selected and the chromogens are mixed together in the indicated amounts. In the context of carbonless copy systems, the chromogenic mixtures will generally by dissolved in an appropriate organic oil vehicle that is then microencapsulated and coated as a CB. Any of the numerous organic solvents or oils generally known in the carbonless art may be used to make a colorless marking liquid composition with the inventive chromogenic mixtures, e.g., diisopropyl napthalene, diaryl ethane and diaryl methane.
EXAMPLE 1
A chromogenic mixture was prepared containing 35% 6'-diethyl amino, 1',3'-dimethyl fluoran, 20% crystal violet lactone, and 45% 2'(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino)fluoran based on the total weight of the chromogenic mixture. This mixture was then dissolved in an appropriate organic solvent in an amount of approximately 7% by weight based on the total weight of the solution to form a colorless liquid marking composition. This marking composition was microencapsulated, coated on paper as a CB and then imaged against a CF coated with zinc-modified phenolic resin as the reactive acidic material. The absorbance values shown in Table 1 were obtained on the Bausch & Lomb Opacimeter and the Hunter colorimeter for the formed images.
TABLE 1______________________________________B & L OPACIMETER HUNTER COLORIMETERImmediate 20 min. 24 hr. L a b______________________________________76.8 44.7 36.3 54.0 +4.4 -6.0______________________________________
The liquid marking composition also exhibited absorbance throughout the visible range, approximately 400 to 700 millimicrons, as shown in FIG. 1.
EXAMPLE 2
A second chromogenic mixture was formed with 24% 6'-diethylamino, 1',3'-dimethyl fluoran, 16% crystal violet lactone, and 60% 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran based on the total weight of the chromogenic mixture. This chromogenic mixture was then dissolved in an appropriate organic solvent to form a colorless liquid marking composition having approximately 6% chromogenic mixture based on the total weight of the solution. The solution was also microencapsulated, coated on paper as a CB and then imaged against a CF coated with zinc-modified phenolic resin to form "black" appearing images. The images yielded the values shown in Table 2 on the B & L Opacimeter and the Hunter colorimeter.
TABLE 2______________________________________B & L OPACIMETER HUNTER COLORIMETERImmediate 20 min. 24 hr. L a b______________________________________73.9 41.2 34.1 53.4 +4.4 -4.9______________________________________
As shown in FIG. 2, the liquid marking composition showed absorbance throughout the visible range upon spectrophotometric analysis. Similar tests have been performed with 2'-t-butyl, 6'-diethyl amino fluoran and 6'-diethyl amino, 3'-methyl fluoran yielding similarly satisfactory results. Thus, the inventive chromogenic mixtures form "black" images of suitable commercial intensity when imaged against CF sheets coated with zinc-modified phenolic resins.
It is to be understood that the above description of the preferred embodiments is not intended to limit the scope of the present invention. Rather, many embodiments not specifically discussed above fall within the spirit of the invention and scope of the claims that follow.
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A chromogenic mixture capable of forming a black image with zinc-modified phenolic resins is disclosed that includes an orange chromogen, a green or single component black chromogen and a blue, indigo or violet chromogen.
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FIELD OF THE INVENTION
The invention relates to a press tool for pressing a receiving part of an installation element onto a pipe pushed into the receiving part, the receiving part pressed on having a section with an outer shape curved constantly in the circumferential direction and within a predetermined shape tolerance.
BACKGROUND OF THE ART
For joining of an installation element—for example of a fitting or of a connecting piece—to a pipe by coldforming, the press tool is placed around a receiving part of the installation element. Drive forces are introduced into the press tool via a drive device, with the result that compressive forces are exerted by the press tool on the receiving part into which the pipe has been inserted. As a result of the compressive forces, the receiving part is formed in such a way that the receiving part is nondetachably joined to the inserted pipe by being pressed on.
As a rule, in addition to at least one press-on section for transmitting longitudinal and torsional forces, a receiving part also has a sealing section for sealing the joint, with the result that such a receiving part can be pressed onto a pipe to form a seal. In the case of joints of relatively small nominal diameters DN (Deutsche Norm [German standard]), a narrow impression region having a polygonal base shape is provided for mechanical securing of the joint.
The sealing of the joint between pipe and installation element is achieved, as a rule, by means of a gasket which faces the pipe and is arranged on the inside of the sealing section of the receiving part. For secure and reliable sealing, firstly an elastic compressive stress of the gasket, distributed uniformly all round, against the pipe and against the receiving part and, secondly, avoidance of crushing of the gasket are absolutely essential. Such a uniform compressive stress can be achieved only if, when the receiving part is being pressed on, the sealing section is formed uniformly all round within a very specific circumference. Manufacturers of such installation elements therefore specify shape tolerances predetermined in a type-specific manner, for example roundness or cylindrical tolerances, for pressed-on receiving parts. The shape tolerances relate in particular to the respective outer shape of the sealing region or optionally also of the entire press-on region.
Inter alia, scissors-like jointing clamps which open in a mouth-like manner at one end and are firmly connected to a drive device at the other end are known in practice for pressing pipe joints having nominal diameters DN up to 54 mm to give a seal. For larger nominal diameters DN, as a rule press chains or even press rings are used which have to be uncoupled from the coordinated drive device each time they are placed on an installation element to be pressed on.
DE 93 14 054 U1 discloses a jointing clamp for pressing pipe joints. The jointing clamp has two press levers, at one end of each of which a substantially rigid press jaw is provided and which in each case are mounted by means of an axle so as to be pivotable in opposite directions on connecting plates. When the tool is in the closed state, a substantially cylindrical press shape which is incorporated into the pressed object during pressing is formed by the two press jaws. Owing to the given dimensions of such jointing clamps, it has been found in practice that the handling is inconvenient where space is limited, in particular in the production of pipelines for household installations, and is often not possible at all in the case of preinstalled fittings close to the wall or close to the floor. In addition, particularly close to the floor, there is the danger that small objects or building site rubble may prevent complete closing of the jointing clamps, which may result in malfunction of the pipe joint. Since, in addition, the end pieces of the jointing clamp which open in a mouth-like manner can be seen only with difficulty by the operator, jointing clamps in which a special device for monitoring for complete closing of the two press jaws is provided are known.
BRIEF SUMMARY OF THE INVENTION
It is an object of the invention to eliminate deficiencies of the prior art and to provide a press tool which safely and reliably permits pressing of an installation element onto a pipe to give a seal, even at small distances from wall and floor surfaces.
Further alternative or advantageous developments and further developments of the invention are described herein.
A press tool for pressing a receiving part of an installation element onto a pipe inserted into the receiving part has two press elements which are connected so as to be movable relative to one another. The receiving part has at least one section which is formed by the press-on process in such a way that the pressed-on section has an outer shape which is curved substantially constantly in the circumferential direction and is within a predetermined shape tolerance, for example a roundness tolerance or a cylindrical tolerance. Each of the two press elements has, on the side facing the respective other press element, a press region which is coordinated with the section.
When the press tool is in the opened state, at least two coordinated end pieces of the press elements are far enough away from one another that the press tool can be pushed over the receiving part and placed on the receiving part. For pressing on the receiving part, drive forces, by means of which the end pieces are moved towards one another, are introduced into the tool. As a result of the press elements resting against the receiving part being moved towards one another, the receiving part is pressed onto the pipe with coldforming. The press-on process is complete when the end pieces coordinated with one another abut one another—the press tool travels to the blocking position—and are thus in the closed state.
According to the invention, at least one of the two press elements is elastically deformable, in particular elastically bendable, in such a way that, under the forces acting on the press element and changing during the press-on process, the shape of its pressing region changes. The pressing region which is exposed in the stationary state of the press tool is present in the circumferential direction in a shape curved differently compared with the outer shape. On the other hand, the same pressing region is present in the circumferential direction in a substantially constantly curved shape corresponding to the outer shape if the pressing region rests against the section when the closed press tool is in the pressing state.
It is known that installation elements and pipes are manufactured from materials which spring back more or less elastically after a plastic deformation. When the closed press tool is in the pressing state, the pressing region adjacent to the section therefore does not have the identical curvature but a correspondingly slightly stronger, substantially constant curvature. This prevents the outer shape of the section from being outside the shape tolerance after the end of the press-on process.
A press element according to the invention is no longer formed so as to be virtually rigid but is elastically deformable under loads which act on the press element during pressing. The elastic deformations, which are caused by the drive forces, by forces exerted by the connection of the two press elements and by forces exerted by the receiving part to be pressed onto the press element, are taken into account specifically in the design of the press element, in particular in the shaping of the pressing region. For this reason, the curvature of the pressing region exposed in the stationary state also differs from the constant curvature of the required outer shape of the pressed-on section. Since, in a press element according to the invention, elastic deformations are intended instead of high rigidity, it is possible to provide smaller, slimmer and lighter press tools, by means of which receiving parts can be pressed onto pipes whose sections are reproducibly within the required shape tolerance.
A variable shape of the pressing region during the press-on process additionally offers possibilities of independently and specifically influencing the press-on process. If, when the receiving part is being pressed on, the sum of the formability required for pressing on and of the work required for the elastic deformation of the press element is distributed as uniformly as possible over the distance covered by the drive forces during pressing on, any resultant peak values of the drive forces can be reduced in a targeted manner. On the one hand, the durability and long-term dimensional stability of press tools can be positively influenced thereby. Advantages in the dimensioning of such press tools are also associated therewith. On the other hand, such press tools can also be operated with a less powerful drive device.
In the case of elastically deformable press tools, there is a direct interdependence between the dimensioning of the press element and the shaping of the pressing region. The shape for such an elastically deformable press element can be obtained either by complicated calculations or by iterative testing and correction of the respective press element, in particular of its pressing region. Thus, a start of the press-on process in regions parallel to the closing plane of the press tool through the central part of the pressing region and subsequent bending together of the press element, which initiates forming by the two edge parts of the pressing region, have proved to be a sequence of individual forming steps which achieves the object. By stepwise correction of the shape of the pressing region by a part of the determined deviations from the required outer shape of the pressing region after the section has been pressed on, the definitive shape of the press region can be determined.
Advantageously, both press elements of a press tool are formed in the same manner, elastically deformable according to the invention, so that the pressing regions thereof when the tools are in the closed state assume a shape corresponding to the required outer shape only under the mechanical loads occurring during pressing on.
In a preferred embodiment of the invention, both press elements are formed so as to be sickle-shaped and are hinged to one another at one end by means of a single bearing pin. At the other end, both press elements have an end piece with in each case a force input region and a stop surface for blocking of the tool travel. This embodiment is distinguished by a simple design and by a precisely guided movement of the two elastically bendable press elements.
In addition to a constantly curved section for a sealing element, a receiving part of an installation element has, as a rule, a further section for nondetachable joining of the installation element to a pipe. For example, in the case of receiving parts of relatively small nominal diameters, a further impression region which is shaped into a hexagon is often provided. For medium and large nominal diameters, such a further section for nondetachable joining often also has a constant curvature, optionally with a cylindrical shape, in the pressed-on state. A corresponding press element has a further pressing region coordinated with the further section, in the shaping of which pressing region the elastic deformation of the press element should likewise be taken into account.
In the case of a hinged press tool having sickle-like press elements, a simple embodiment envisages the respective pressing regions will be formed by a plurality of segments which are arranged in series and which have in each case a constant curvature in the circumferential direction and are arranged in series tangentially, with the result that their centres of curvature are a distance apart. In the case of such a press tool, in the stationary, closed state of the exposed pressing regions, a rest shape is formed which differs from the outer shape and whose internal diameter perpendicular to the closing plane of the press tool is smaller than its internal diameter substantially parallel to the closing plane.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Embodiments of the invention are explained in more detail below with reference to figures.
FIG. 1 shows an oblique view of a press tool according to the invention, which, in the pressing state, is pressing a fitting onto a pipe,
FIG. 2 shows another oblique view of one of the two press elements of the press tool from FIG. 1 ;
FIG. 3 shows a detailed view of the closed press tool from FIG. 1 in the rest state with the two pressing regions in section and
FIG. 4 shows a diagram illustrating the difference between the inner profiles of the same press element in the rest state and in the pressing state of a closed press tool.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows an installation element which is in the form of a fitting 2 and into one end of which a pipe 3 is inserted, and an embodiment of a press tool according to the invention, which is placed against the fitting 2 , in an oblique view.
The press tool shown here has two press elements 5 , which are identically formed here and have an elongated sickle-like basic shape. A force input region 17 and a stop surface 20 are provided at one end of each of the two press elements 5 . A tension jaw, which in turn is connected to a drive device, may be applied to the two force input regions 17 . Two drive forces are exerted on the press tool by the tension jaw for pressing the fitting 2 onto the pipe 3 . At the other end, the two press elements 5 are hinged to one another by means of a common bearing pin 18 .
The fitting 2 shown here is a KIWA-DVGW copper fitting of nominal diameter DN 18 from system supplier “Viega, Franz Viegner II, D-57428 Attendorn”. The fitting 2 , has at both ends, a receiving part 1 which is formed here in each case for a pipe 3 of the same nominal diameter. The pipe 3 , for example a copper pipe having a wall thickness of one and a half millimeters, is inserted at one end in the fitting 2 up to a stop provided in said fitting.
That receiving part 1 of the fitting 2 which is visible in FIG. 1 is in the initial state where it has not been pressed on and thus has a rotationally symmetrical basic shape. When the receiving part 1 has not been pressed on, a pipe 3 has not yet been inserted. The receiving part 1 has a sealing section 4 , which in this case is a bulge in the form of half a torus, two press-on sections 21 , which are arranged on both sides of the sealing section 4 , and two impression sections 22 , which in each case are arranged adjacent to one of the press-on sections. The sealing section 4 has, on its inside, an all-round bulge which is likewise toroidal and in which a gasket 19 , shown here only in part, is provided.
The other receiving part—for the most part concealed in FIG. 1 by the applied tool—is in the initial state before being pressed on. The press tool grips almost completely around the other receiving part and rests against it. As a result of the drive forces, the press tool can be brought into the pressing state. The two drive forces are exerted on the force input regions 17 by a tension jaw which is applied to the tool and is not shown in FIG. 1 .
By means of the two drive forces, which in this embodiment may have, for example, a magnitude of 60,000 to 65,000 Newton, the two press elements 5 are moved towards one another until the two hinged end pieces of the press elements 5 abut one another with their stop surfaces 20 .
Due to the two press elements 5 moving towards one another, forming forces are exerted extensively over the receiving part 1 to be pressed on, with the result that said part is formed by plastic deformation and is pressed onto the pipe 3 so that it is nondetachable. Owing to the mechanical loads acting on the tool during forming of the other receiving part, the two press elements 5 are elastically deformed since—in comparison with the substantially rigid press jaws of a conventional jointing clamp—they have substantial, elastic flexibility under the resultant loads, owing to their dimensioning. The extent and the form of the elastic deformation of the respective press element 5 are determined by its rigidity, the drive force introduced at one end, the force exerted at the other end by the common bearing pin 18 and the forces with which the receiving part to be pressed on resists the forming.
The two press-on sections 21 and the two impression sections 22 are formed here to give a cylindrical or hexagonal shape, respectively, during pressing on by the press tool. The press-on sections 21 form a frictional connection, and the impression sections 22 an interlocking connection, with the pipe 3 . By means of the hexagon impressed into the fitting 2 and the pipe 3 , joints of small nominal diameters DN are generally prevented from being pulled apart by small and medium tensile forces. In the case of larger nominal diameters DN, a cutting ring secures the joint with respect to larger tensile forces, said cutting ring being arranged as a rule between a fitting and a pipe inserted into said fitting. A receiving part of such a fitting has a securing region which is arranged around the cutting ring and is formed during pressing on in an outer shape within a predetermined cylindrical tolerance and thus exerts a specified compressive force on the cutting ring.
On the other hand, when the fitting 2 is being pressed onto the pipe 3 , the toroidal bulge of the sealing section 4 is formed toroidally in such a way that the gasket 19 is elastically deformed in a controlled manner between the pipe 3 and the bulge and is thus prestressed to a defined extent. The elastically prestressed gasket 19 exerts compressive stresses on the pipe 3 on the one hand and on the bulge on the other hand. The compressive stresses exerted by the gasket 19 are of very decisive importance for the tightness of the joint.
When the two stop surfaces 20 of the press elements 5 , driven by the drive forces, are caused to abut one another—the press tool travels to the blocking position—the press-on process is complete and the fittings 2 are joined nondetachably and with a seal to the pipe 3 via the pressed-on receiving part 1 .
The quality and the reliability of the joint between an installation element and a pipe can be assessed in a manner known per se through the dimensions of the outer shape of the pressed-on receiving part 1 . If the distance across flats of the hexagons which are impressed into the impression regions 22 is within a value range from 23.1 to 23.6 millimeters, a specified pull-apart value for the compression joint is guaranteed by the manufacturer. If the dimensions of the outer shape of the sealing section 4 of the pressed-on receiving part 1 are within a predetermined shape tolerance, the tightness of the joint can be assessed on the basis of the elastic deformations of the gasket 19 and hence on the basis of the compressive stresses exerted on the fitting 2 and the pipe 3 by said gasket. If the outer shape is outside a specified shape tolerance, proper functioning of the installation element is no longer guaranteed by the manufacturer. In this embodiment, for example, a roundness tolerance having a lower and an upper diameter of 24.7 and 25.2 millimeters, respectively, is specified by the manufacturer for the summit region of the toroidal bulge.
FIG. 2 shows the upper press element 5 of the press tool from FIG. 1 in an other oblique view. The press element 5 has, at one end, the end piece with the stop surface 20 and the force input region 17 visible only in FIG. 1 . At the other end, it has a joint part 23 in which a receiving hole for the bearing pin 18 shown only in FIG. 1 is provided. Between the stop surface 20 and the joint part 23 , the press element 5 here has, on the side facing the other press element, a toroidal pressing region 7 , two cylindrical pressing regions 24 and two hexagonal pressing regions 25 , adjacent to both ends of which in each case there is a planar end region 26 , which is smaller here. The end regions 26 are formed by additional recesses in the press element 5 . Those ends of the end regions 26 which face away from the pressing regions 7 and 24 are each provided with a radius.
Here, the press element 5 is shown in the rest state with exposed pressing regions. A first pressing region 7 can be assigned to the sealing section 4 from FIG. 1 and has a two-dimensionally curved shape which in this case has three different curvatures in the circumferential direction. The two cylindrical pressing regions 24 , which in each case can be assigned to one of the press-on sections 21 from FIG. 1 , are arranged on both sides of the first pressing region 7 . They have a one-dimensionally curved shape, likewise with three different curvatures here. Arranged adjacent to two cylindrical pressing regions 24 are the hexagonal pressing regions 25 , which have the conventional shape of half a hexagon and can be assigned to the impression region 22 from FIG. 1 . The planar end regions 26 arranged between each of the pressing regions 7 and 24 and the stop surface 20 on the one hand and the joint part 23 on the other hand have different lengths here.
FIG. 3 shows a detailed view of the closed press tool from FIG. 1 in the rest state with the exposed pressing regions 7 , 24 and 25 and the adjacent end regions 26 in sectional view. The pressing regions 7 , 24 and 25 and the respective end regions 26 of the two press elements 5 are arranged in each case with mirror symmetry across the closing plane 6 . Since, in the rest state, the tool is not subjected to any mechanical loads, the press elements 5 and their exposed pressing regions 7 , 24 and 25 are also not elastically deformed.
The toroidal pressing region 7 is formed here by a central segment 10 , a segment 11 on the joint side and a segment 12 on the stop side, which in each case have tangential transitions with one another. The individual segments 10 , 11 and 12 each have different curvatures in the circumferential direction. The central segment 10 extends over an angular range of 120° and is thus several times the size of the segment 11 on the joint side and of the segment 12 on the stop side, which extend here over an angular range of about 22° each.
While here the central segment 10 has a central radius 14 of curvature of 12.35 millimeters in the circumferential direction in the summit region of the torus, the segment 11 on the joint side and segment 12 on the stop side have a corresponding radius 15 or 16 of curvature, respectively, of 12.45 or 12.55 millimeters on the joint side and stop side, respectively. In addition, the centre of the central radius 14 of curvature has a centre offset 13 of 0.3 millimeters on each side of the closing plane 6 , with the result that—in the rest state of the tool—the banana shape of the toroidal pressing region 7 is additionally reinforced. The centres of the radii 15 and 16 of curvature on the joint side and on the stop side are likewise on each side of the closing plane 6 . As a result of this special shape of the two toroidal pressing regions 7 , the internal diameter in the opening direction 8 in the case of a closed press tool, i.e. perpendicular to the closing plane 6 , is substantially smaller than the internal diameter transverse to the opening direction 9 , in this case inclined about 15° to the closing plane 6 .
The cylindrical pressing region 24 , which can be assigned to the press-on section 21 of the receiving part 1 from FIG. 1 , likewise has three analogous segments with in each case corresponding, different radii of curvature, the centres of which here coincide with the centres of the radii of curvature of the toroidal pressing region 7 . The third pressing region 25 is in the form of half a hexagon.
In contrast, the pressing region of a conventional, rigid press jaw of nominal diameter DN 18—e.g. a “press jaw 18 , model No: 22992; Viega, Franz Viegner II, D-57428 Attendorn”—has a single constantly curved segment having a radius of curvature of 12.35 millimeters. In the rest state, the shape of such a pressing region is therefore already within the required shape tolerance of the outer shape of a pressed-on receiving part.
FIG. 4 shows a comparison to scale of the inner profile of the same press element in the rest state and in the pressed-on state of a closed press tool. A continuous line 27 represents the inner profile of the press element in the rest state with an exposed pressing region. A broken line 28 on the other hand represents the inner profile of the same press element in the pressed-on state of the closed tool. By means of such a press tool, a receiving part having a sealing section and a press-on section of a “Geopress fitting 20-63” of nominal diameter 50 can be pressed on within the same cylindrical tolerance. The pressing region of the press element in the pressed-on state of the closed tool rests against the sealing or press-on section, which is not shown in FIG. 4 . In the pressing region, the broken line 28 has a substantially constant curvature which corresponds to the constant curvature of the required outer shape of the pressed-on sealing section or press-on section.
Between the two inner profiles, the maximum difference at the summit of the pressing region in the opening direction is slightly more than half a millimeter. This does not quite correspond to one percent of the nominal diameter of the compression joint. The difference between the internal diameters in the closing plane of the press tool has a value of slightly more than two millimeters, which corresponds to about 4 percent of the nominal diameter.
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A press tool for pressing a receiving part of a fitting onto a pipe is provided. The press tool includes two elastically-deformable press elements, each having a first end, a pressing region, assigned to the sealing section, having an inner shape that at least partially departs from a constant curvature in a circumferential direction, and a second end having a force input region and a stop surface. A hinge couples the press elements together at the first end of each press element. When the press tool is closed, the stop surfaces of the press elements abut one another, and when the press tool is closed and a pressing force is applied to the force input regions of the press elements, the press elements elastically deform such that the inner shapes of the pressing regions are substantially constantly curved in the circumferential direction.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a continuation of pending U.S. patent application Ser. No. 12/468,162, that is entitled “POWER ROLLER SCREED WITH MULTIPLE SCREED ROLLERS,” and that was filed on May 19, 2009, which is a continuation application of U.S. patent application Ser. No. 12/014,383, that is entitled “POWER ROLLER SCREED WITH MULTIPLE SCREED ROLLERS,” and that was filed on Jan. 15, 2008 (now U.S. Pat. No. 7,544,012), which is a divisional application of U.S. patent application Ser. No. 11/299,064, that is entitled “ARTICULATING REVERSIBLE POWER SCREED WITH A VARYING LENGTH ROLLER,” and that was filed on Dec. 9, 2005 (now abandoned). Priority is claimed to each of these three patent applications, and the entire disclosure of each of these three patent applications is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an improvement in the methods used to level and finish freshly poured concrete slabs. More specifically, to a powered screed apparatus having an elongated cylindrical roller that is composed of connecting sections of varying length allowing for the use of the apparatus with concrete slabs of varying widths. Additionally, this screed apparatus contains components that enable it to be further adapted to be used with concrete slabs of differing shapes and profiles.
BACKGROUND OF THE INVENTION
[0003] Concrete slabs are ubiquitous in today's world. From highways to airport runways to parking lots to building floors, sidewalks, and driveways, concrete slabs faun the durable surfaces we depend on for modern life. The methods used to construct all these differing structures are essentially the same in that they all require that the wet concrete mixture be poured into a form and a mechanism by which the concrete can be leveled and compacted.
[0004] In its simplest form, this process is accomplished by the use of wooden forms, most commonly 2 by 6 or 2 by 8 material, that is positioned in a parallel manner at the desired width. This form then operates to contain the poured concrete in a lateral area that is to be covered by the concrete slab. When the required amount of concrete is thus positioned, it is then necessary to level it off to the height of the forms. It is this later process in which the screed is employed. In this method the leveling process is accomplished by moving a flat piece of material spanning the two parallel forms in a back and forth manner. This operation serves to move any of the excess concrete that extends above the upper surfaces of the forms either into any low areas or off of the prospective slab altogether.
[0005] While the manual method described above works well enough on small jobs such as the repair of short sections of sidewalk, it has numerous deficiencies. The first of these is, that even in small jobs, it is labor intensive and therefore costly over the long term. Additionally, the use of a manual screed is not very effective at distributing and compacting the concrete within the form therefore producing a finished slab of a lesser quality than is generally desired. More importantly, the manual screed is effectively useless in larger jobs where wide slabs of concrete are required.
[0006] Many of the problems associated with the use of manual screeds have been solved by the use of powered models. The power screeds available today come in two general forms. The first of these generally consist of a flat screed bar that is attached to a motorized articulation apparatus. In use, the screed bar fits over existing forms in much the same manner as the manually operated screed. The screed bar is then moved back and forth over the concrete by the articulation motor. While this system solves some of the problems associated with screeds, especially in larger jobs, it is cumbersome both in construction and operation.
[0007] The other type of powered screed is referred to as a powered roller screed. The powered roller screed generally consists of an elongated tube that is rotationally driven by an attached motor. In operation, the roller tube is positioned over the raw concrete at a position on the upper edges of the forms. The roller tube is then moved along the top of the forms in a direction that is opposite the rotational motion of the roller tube at its point of contact with the concrete. This apparatus produces a smooth and flat finish to the concrete and is generally considered to be the preferred method in the industry today.
[0008] While the powered roller screeds described above are effective, they do suffer from a number of operational deficiencies. The first of these is that they are designed and built in fixed lengths and are therefore not adjustable to accommodate concrete pours of varying widths. While this is not a huge problem, it results in the use of screed apparatuses that extend well over the forms making them difficult to maneuver at the job site.
[0009] Another problem with the powered roller screeds of the prior art is that they offer no way to compensate for special application concrete pours. It is often desirable to pour a concrete slab that either has a ridge or valley running longitudinally through its center. This form of concrete slabs is an effective way of controlling water with respect to the surface of the slab. The prior art consists entirely of screed apparatuses that have rigid rolling tubes. Therefore, in the past the only way of constructing ridges or valleys in concrete slabs was to pour each side of the slab independently. While this method works, it is more time consuming than it would be to perform the entire pour in one pass.
[0010] A further problem existing in the prior art is that they provide no reasonable means by which an extremely wide concrete pour can be accomplished as a single operation. This problem arises because the power sources are not powerful enough to drive long sections of screed roller tubes. A possible solution to this is to place a power unit on either side of the roller tube. For this approach to work, however, the power units must be capable of operating in opposite directions and their rate of rotation must be matched exactly. While possible, these requirements of such an apparatus make it impractical to build and operate such an apparatus.
[0011] A still further problem in the prior art is the inability of screed apparatuses to operate effectively in construction circumstances that require a circular concrete slab. Circular concrete slabs are commonly used in the construction of grain silos and other similar buildings. In the past the only way to finish these types of slabs was to run a screed apparatus over the pour from one end to the other or to manually rotate it around the pour. These methods work but produce results that are less than desirable.
[0012] From the forgoing discussion it can be seen that is would be desirable to provide a screed apparatus that is easily adjustable in the length of its roller thereby allowing it to be fitted to specific job applications. Additionally, it can be seen that it would be desirable to provide a screed apparatus that is capable of flexing to accommodate concrete pours containing ridges or valleys. It can also be seen that it would be desirable to provide a screed apparatus that is capable of operating in extremely wide concrete pours. Finally, it can be seen that it would be desirable to provide a screed apparatus that can be operated effectively in the finishing of circular concrete slabs.
SUMMARY OF THE INVENTION
[0013] It is the primary objective of the present invention to provide a powered roller screed apparatus that has the capacity of adjusting the length of the roller member to accommodate concrete pours of varying widths.
[0014] It is an additional objective of the present invention to provide such a powered roller screed apparatus that employs an articulating roller member allowing for its use with concrete pours having a ridge or valley extending down its longitudinal center.
[0015] It is a further objective of the present invention to provide such a powered roller screed apparatus that can employ the use of a roller member that has a center counter rotational assembly allowing for the use of two rotational drive motors on either end of the roller member thereby providing a means by which extremely wide concrete pours can be effectively accomplished.
[0016] It is a still further objective of the present invention to employ such a powered roller screed apparatus that can employ the use of a roller member that can be rotationally anchored at the center of a circular concrete pour thereby providing a means by which such slabs can be effectively finished.
[0017] These objectives are accomplished by the use of a powered rotational screed apparatus having a screed roller member that is adaptable to accommodate any number of specialized concrete slab pouring applications. The present invention is designed generally to facilitate the finishing process necessary in the formation of concrete slabs. In the accomplishment of this process, the present invention is deployed on a slab pour site in a manner so that its screed roller member comes into contact with both the upper surfaces of the concrete forms and the unfinished concrete contained therein. This is accomplished by extending the screed roller member between the forms and over the area where the slab is to be formed.
[0018] One end of the screed roller member is rotationally attached to the drive assembly and the other to a pull rope. The drive assembly is the component of the present invention that houses the drive motor which in turn provides the rotational power necessary to operate the present invention. The drive motor is fixed within the drive assembly by the use of the motor frame which also provides the point of fixed attachment of the handle assembly. The handle assembly extends upward from the motor frame to position the control handle and pulling handle in a location so that the entire drive assembly can be easily controlled by an operator. The other end of the screed roller member provides the point of attachment for the pull rope through the operation of a pull bearing. The pull bearing operates to isolate the pull rope from the rotational aspects of the screed roller member allowing it to be fixedly attached to the pull rope.
[0019] To perform the finishing operation, the drive motor is engaged which in turn powers the screed roller member. As the screed roller member spins, the drive assembly operator and the pull rope operator move the present invention in a direction that is opposite to the rotation of the screed roller member over the unfinished concrete. This action has been found to be effective in producing the desired finish on the upper surface of the slab while also causing the concrete to compact in the necessary consistency.
[0020] The drive assembly of the present invention is made up of a handle assembly that is attached at its proximal end to a drive motor frame. The drive motor frame houses the drive motor that provides the rotational force for the operation of the present invention. The handle assembly serves to position the control handle and the pull handle in a position so that they may easily be grasped and manipulated by the operator. Additionally, the control handle contains the switch that controls electrical power to the drive motor.
[0021] The output of the drive motor is configured so that it can be fitted to a drive socket which is of a common impact type. This in turn allows for the attachment of the drive plate assembly which in turn bolts to the proximal end of the screed roller member. The screed roller member is the elongated cylindrical component of the present invention that is used to perform the finishing operation that is the object of the present invention.
[0022] The screed roller member is made up of three primary components. The first of these is the tube body which is a tube of the desired inside and outside diameter and is generally composed of a high strength aluminum alloy. Aluminum is used in this application due to its desirable strength to weight ratio. The other components are the female and male attachment plugs. The female and male attachment plugs are relatively short cylindrical components having a shoulder of an identical outside diameter of the tube body and an engagement body that has an outside diameter that is equal to the inside diameter of the tube body. The screed roller member is formed by fixedly attaching one female and one male attachment plug to either end of the tube body. The female and male attachment plugs also contain a threaded hole that passes longitudinally through their center. The threaded hole allows for the placement of a threaded rod in a position so that it extends out beyond the outside end of the male attachment plug to which it is fixedly attached. Additionally, the female attachment plug is designed with a recess that extends into its body at the initial segment of its threaded hole. Conversely, the male attachment plug is designed with a similarly positioned shoulder that fits within the recess of the female attachment plug. Thus, the threaded rod and the recess and shoulder components of the female and male attachment plugs provide a means by which two or more screed roller members can easily and securely connect to one another. Also, this design provides a means of attaching additional components that will be discussed in greater detail below.
[0023] The above described method of constructing the screed roller members provides a means by which the present invention can be adapted to match the width of all possible concrete pours. This is facilitated by the building of screed roller members of varying lengths that can then be quickly and easily added or removed to achieve the desired length. The operator then simply connects the desired screed roller members by the use of the threaded rod and threaded hole and secures them together by the use of a securement bolt which extends through the body of the female attachment plug and engages the threaded rod contained therein.
[0024] The present invention is also capable of being employed to finish a concrete slab that has either a ridge or valley running longitudinally though its center. This is accomplished by the use of the articulation member. The articulation member is a self-contained device that is designed to be fitted between two screed roller members. The placement of the articulation member in this manner allows the connected screed roller members to vary in their longitudinal axis with respect to one another thereby allowing the present invention to finish a concrete slab that contains either a central ridge or valley.
[0025] The articulation member contains two primary components that make this possible. The first of these is a centrally located U-joint that is fixedly attached at either end to the two joined screed roller members. The U-joint employed in this application is of a type that is commonly in automotive or other vehicle applications and allows the two screed roller members to rotate around slightly different longitudinal axises. The U-joint is located in a central cavity of the female and male articulation bodies which operate to tie the articulation member to the screed roller members.
[0026] The second component of the articulation member is the pull bearing assembly. The purpose of the pull bearing assembly is to provide an external surface within the screed roller member which is rotationally stationary when the bulk of the screed roller member is rotating during use. This is accomplished by the incorporation of an outer bearing body that is isolated from the remaining components by a bearing. The use of the pull bearing assembly in this application allows the articulation member to interact with a center support that is incorporated within the pour forms. The center support is positioned longitudinally within the form at the position where the center of the ridge or valley is to be located. The articulation member then runs along the top of the center support thereby finishing the concrete at the levels dictated by the forms and the center support.
[0027] An additional component provides the present invention with the capability of finishing wide concrete pours. This is the counter rotation member that, like the articulation member described above, fits between and connects two sections of screed roller members. The counter rotation member provides a means by which these two screed roller members can be rotated in opposite directions during finishing operations. This is necessary in wide pours because the drive motors normally employed in screeding concrete are not powerful enough to provide the rotational force to long sections of screed roller members. The use of the counter rotation member allows for the placement of an additional drive assembly in place of the pull rope thereby providing the power to finish wide concrete pours.
[0028] The counter rotation member is constructed in a similar manner as described above for the articulation member in that it contains a bearing that rotationally isolates an outer bearing body from the rotation of the screed roller members. Additionally, the counter rotation member also isolates the rotation of the two screed roller members attached to it from one another. This is accomplished by the internal structure of the counter rotation member in that its two primary components are the female and male counter rotation bodies. These two components serve to connect the counter rotation member to the screed roller members. Additionally, each of these is equipped with an inner flange which are rotationally isolated from one another by a pair of isolation bearings. This configuration provides the means by which the two screed roller members can rotate in opposite directions thereby allowing the present invention to finish wide concrete pours.
[0029] Another optional component of the present invention that adds flexibility to its operations is the center anchor member. The center anchor member allows the present invention to finish circular concrete pours such as those used in the construction of grain silos and other similar buildings. The center anchor member allows the non-powered end of the screed roller member to be properly anchored in the center of the concrete pour and to rotate freely therein.
[0030] The center anchor member is made up of a stationary outer ring that is fixedly attached at its lower end to an anchor rod and at its upper end to a handle. The anchor rod serves to provide the rotational attachment to the anchor tube that is positioned in the desired location with respect to the concrete slab.
[0031] The outer bearing ring also provides for the pivotal attachment of the bearing that allows for the attachment of the screed roller member that is accomplished by the use of an extending threaded rod and a centering securement nut. The pivotal nature of the attachment of the bearing also allows for the altering of the angle of attachment of the screed roller member providing a means by which an angled pour of the concrete can be accomplished for much the same reasons as described above for the articulating member.
[0032] A still further attachment for the present invention is provided that allows for the finishing of a concrete slab in a situation where it is desirable to construct a concrete slab adjacent to an existing one with an upper surface that is slightly lower than the existing one. This application is most common in the pouring of a driveway up to a garage slab. This attachment consists of an existing slab drop-down member that is attached to the non-powered end of a screed roller member. The existing slab drop-down member is attached in much the same manner as described above for other components of the present invention in that it contains an isolated bearing and an outer pull ring. This allows for the attachment of a pull rope on the non-powered end of the screed roller member that provides a means of controlling this end of the screed roller member.
[0033] Finally, the existing slab drop-down member has an extending drop-down body that has an outside diameter that is smaller than that of the screed roller member. This drop-down body allows for the finishing of a concrete slab that is lower than the existing slab thereby creating the desired relationship between the two concrete slabs.
[0034] A yet further attachment for the present invention is the footing member. The footing member provides the present invention with the capability of finishing a concrete slab that is used to form the floor of a basement where the footings and walls are already constructed. The footing member is made up of a footing member body that is attached to the non-powered end of a screed roller body in the same manner as described for the previous attachments using an outer bearing body and bearing configuration. Additionally, the footing member is equipped with a ring spacer. The ring spacer is a circular plate that is inserted into the footing member in a location so that it effectively raises the screed roller member up off of the footing. This design allows for the simplified pouring of such a concrete slab up to the wall and over the footing to properly construct a basement floor.
[0035] The final attachment for the present invention in terms of this discussion is the vibration compacting member. The vibration compacting member operates to enhance the present invention's concrete compacting effect of the unfinished concrete slab. This is accomplished by the employment of a device that is commonly used in the concrete industry known as a stinger. The stinger is made up of a vibrating rod that is inserted into wet concrete and which drives out air pockets contained within the concrete.
[0036] In its use with the present invention, the stinger's vibration drive motor is attached to the drive assembly. The vibration drive motor has a flexible drive rod that extends from it down to the stinger body positioned at the drive end of the screed roller member between the drive plate assembly and the screed body. The attachment of the vibration compacting body to the screed roller member is accomplished by the use of an outer bearing body and stinger bearing assembly in a similar manner as described above for the present invention's previously illustrated attachments.
[0037] The stinger body is made up of a stinger tube and a stinger ring. The stinger body contains the stinger and transfers its vibrational motion to the stinger ring. The stinger ring is in turn attached to the stinger bearing assembly that transfers the vibration to the screed roller member. This design serves to impart a vibrational aspect to the motion of the screed roller member during the finishing operation. This vibration has been found to enhance the compacting of the unfinished concrete as it operates to drive off unwanted the air pockets that are inherent in all concrete pours.
[0038] For a better understanding of the present invention reference should be made to the drawings and the description in which there are illustrated and described preferred embodiments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 is a perspective view of the present invention which illustrates the manner in which it is deployed to finished a slab of concrete.
[0040] FIG. 2 is a top elevation view of the drive assembly component of the present invention illustrating its manner of construction.
[0041] FIG. 3 is a side elevation view of the drive assembly component of FIG. 2 .
[0042] FIG. 4 is a side elevation exploded view of the drive motor and drive plate assembly components of the present invention illustrating the manner by which they engage the screed roller member.
[0043] FIG. 5 is a side elevation view of the screed roller member of the present invention illustrating its general manner of construction and the way two or more can be joined together to form a longer screed roller member.
[0044] FIG. 6 is a side elevation view of a plurality of screed roller members illustrating the varying lengths in which they can be constructed.
[0045] FIG. 7 is a side elevation cut-away view of the connection between two adjoining screed roller members illustrating the methods employed to make the connection.
[0046] FIG. 8 is a front elevation view of the present invention illustrating its use in conjunction with the articulation member to finish a concrete slab having a valley running longitudinally through its center.
[0047] FIG. 9 is a front elevation view of the present invention as configured in FIG. 8 illustrating it as used to finish a concrete slab having a ridge running longitudinally through its center.
[0048] FIG. 10 is a side elevation cut-away view of the articulation member component of the present invention illustrating the manner of construction of its internal components.
[0049] FIG. 11 is a front elevation view of the present invention illustrating its use in conjunction with the counter rotation member to finish a wider that normal concrete slab.
[0050] FIG. 12 is a side elevation cut-away view of the counter rotation member component of the present invention illustrating the manner of construction of its internal components.
[0051] FIG. 13 is a front elevation view of the present invention illustrating its use in conjunction with the center anchor member to finish a circular concrete slab.
[0052] FIG. 14 is a front elevation view of the center anchor component of the present invention illustrating its manner of construction.
[0053] FIG. 15 is a side elevation cut-away view of the center anchor member component of the present invention illustrating the manner of construction of its internal components.
[0054] FIG. 16 is a front elevation view of the existing slab drop-down member component of the present invention illustrating its manner of construction.
[0055] FIG. 17 is a side elevation cut-away view of the existing slab drop-down member component of the present invention illustrating the manner of construction of its internal components.
[0056] FIG. 18 is a front elevation view of the footing member component of the present invention illustrating its manner of construction.
[0057] FIG. 19 is a side elevation cut-away view of the footing member component of the present invention illustrating the manner of construction of its internal components.
[0058] FIG. 20 is a side elevation view of the drive assembly component of the present invention illustrating it as used in conjunction with a vibrational compacting member.
[0059] FIG. 21 is a top elevation view of the drive assembly of FIG. 20 .
[0060] FIG. 22 is a side elevation view of the stinger body of the vibrational compacting member component of the present invention.
[0061] FIG. 23 is a side elevation cut-away view of the vibrational compacting member component of the present invention illustrating the manner of construction of its internal components.
DETAILED DESCRIPTION
[0062] Referring now to the drawings, and more specifically to FIGS. 1 , 2 , and 3 , the powered rotational screed apparatus 10 has a screed roller member 12 that is adaptable to accommodate any number of specialized concrete slab pouring applications. The present invention is designed generally to facilitate the finishing process necessary in the formation of concrete slabs. In the accomplishment of this process, the present invention is deployed on a slab pour site in a manner so that its screed roller member 12 comes into contact with both the upper surfaces of the concrete forms 14 and the unfinished concrete 16 contained therein. This is accomplished by placing the screed roller member 12 between the concrete forms 14 and over the area where the slab is to be formed.
[0063] One end of the screed roller member 12 is rotationally attached to the drive assembly 20 and the other to a pull rope 22 . The drive assembly 20 is the component of the present invention that houses the drive motor 24 which in turn provides the rotational power necessary to operate the present invention. The drive motor 24 is fixed within the drive assembly 20 by the use of the motor frame 36 which also provides the point of fixed attachment for the handle assembly 26 . The handle assembly 26 extends upward through the extension bar 28 from the motor frame 36 to position the control handle 30 and the pull handle 32 in a position so that the entire handle assembly 26 can be easily controlled by an operator. Finally, the power to the drive motor 24 is supplied through the power cord 42 by way of the control handle 30 . The drive motor 24 may also be powered by an appropriate battery (not shown) which may be mounted to the drive motor 24 or extension bar 28 .
[0064] The other end, or the non-powered end, of the screed roller member 12 provides the point of attachment for the pull rope 22 through the operation of a pull bearing assembly 84 . The pull bearing 84 operates to isolate the pull rope 22 from the rotational aspects of the screed roller member 12 allowing it to be fixedly attached to the pull rope 22 . The nature and manner of operation of the pull bearing 84 will be described in greater detail below with reference to other components of the present invention.
[0065] Additionally, the handle assembly 26 of the present invention is equipped with a pivotally mounted stand 34 . The stand 34 allows the drive assembly 20 to be left in an upright position when not in use so that the control and pull handles, 30 and 32 , are in an easily accessible location. When not in use, the pivotal attachment of the stand 34 allows it to be rotated up next to the extension bar 28 so that it is not in the way during the operation of the handle assembly 26 .
[0066] To perform the finishing operation, the drive motor 24 is engaged by the use of the control handle 30 which in turn powers the screed roller member 12 . As the screed roller member 12 spins, the drive assembly 20 operator and the pull rope 22 operator move the present invention in a direction that is opposite to the rotation of the screed roller member 12 over the unfinished concrete 16 . This action has been found to be effective in producing the desired finish on the upper surface of the finished concrete 18 while also causing the concrete to compact to the necessary consistency.
[0067] The output of the drive motor 24 is configured so that it can be fitted to a drive socket 38 which is of a common 6 point impact type as illustrated in FIG. 4 . As the drive socket 38 passes through the motor frame 36 , it is encased by the socket bearing 40 . The socket bearing 40 allows the drive socket 38 to spin freely with the drive motor 24 while securely holding it within the stationary motor frame 36 .
[0068] The use of the drive socket 38 allows for the securement of the drive plate assembly 52 which in turn bolts to the proximal end of the screed roller member 12 . To facilitate this, the drive plate assembly 52 is equipped with a rearwardly extending hexagonal shaft 53 that is specifically designed to engage the internal surface of the drive socket 38 . Additionally, each of these components has an attachment pin hole 58 . The attachment pin holes 58 allow for the passage of an attachment pin (not shown) through the drive socket 38 and hexagonal shaft 53 which secures the two together.
[0069] The drive plate assembly 52 also has a circular drive plate 44 that is of the same outside diameter as the screed roller member 12 . The drive plate 44 allows for the attachment of the drive plate assembly 52 to the screed roller member 12 through the use of a plurality of bolts 54 . Additionally, the distal surface of the drive plate 44 is equipped with a centrally located male shoulder 70 that operates to center the female attachment plug 46 of the screed roller member 12 with reference to the drive plate assembly 52 . This configuration not only transfers the rotational power of the drive motor 24 to the screed roller member 12 , but also ensures that all of the operational components are properly aligned.
[0070] The screed roller member 12 is the elongated cylindrical component of the present invention that performs the finishing operation that is the object of the present invention. The external manner of construction of the screed roller member 12 is illustrated in FIGS. 5 and 6 . The screed roller member 12 is made up of three primary components. The first of these is the tube body 50 which is a tube of the desired inside and outside diameter and is generally composed of a high strength aluminum alloy, although the use of other materials for this purpose is possible. Aluminum is used in this application due to its desirable strength to weight ratio. The other components are the female and male attachment plugs, 46 and 48 .
[0071] The female and male attachment plugs, 46 and 48 , are relatively short cylindrical components having a shoulder of an identical outside diameter of the tube body 50 and an engagement body that has an outside diameter that is equal to the inside diameter of the tube body 50 . The screed roller member 12 is formed by fixedly attaching one female attachment plug 46 and one male attachment plug 48 to either end of the tube body 50 . This forms a complete unit that is then capable of being used individually or in conjunction with another as will be described in greater detail below.
[0072] The above described method of constructing the screed roller members 12 provides a means by which the present invention can be adapted to match the width of all possible concrete pours. This is facilitated by the building of screed roller members 12 of varying lengths that can then be quickly and easily added or removed to achieve the desired length. This design allows for the construction of screed roller members 12 of varying lengths as illustrated by length A, B, C, and D screed roller members, 60 , 62 , 64 , and 66 . Additionally, it must be stated that the lengths of the screed roller members 12 as shown is intended to be for illustrative purposes only and the construction of a screed roller member of any usable length is possible.
[0073] The female and male attachment plugs, 46 and 48 , also contain a threaded hole 74 that passes longitudinally through their center as illustrated in FIG. 7 . The threaded hole allows 74 for the placement of a threaded rod 72 in a position so that it extends out beyond the outside end of the male attachment plug 48 to which it is fixedly attached. This attachment is accomplished by passing an attachment pin 56 through the body of the male attachment plug 48 in a manner so that it engages the threaded rod 72 . In this configuration, the attachment pin 56 is retained within the male attachment plug 48 even when the screed roller member 12 is disassembled.
[0074] The female attachment plug 46 is designed with a centrally located, with respect to its longitudinal axis, female recess 68 that extends into its body at the initial segment of its threaded hole 74 . Conversely, the male attachment plug 48 is designed with a similarly positioned male shoulder 70 that fits within the female recess 68 of the female attachment plug 46 . Thus, the threaded rod 72 , the female recess 68 , and the male shoulder 70 components of the female and male attachment plugs, 46 and 48 , provide a means by which two or more screed roller members 12 can easily and securely connected to one another. Finally, once the proper connection has been accomplished through the described methods, the female attachment plug 46 can be locked in place with reference to the threaded rod 72 . This is accomplished by the use of the securement bolt 76 that passes through the body of the female attachment plug 46 and engages the surface of the threaded rod 72 .
[0075] The connection of two or more screed roller members 12 is then simply accomplished by connecting the desired screed roller members 12 by the use of the threaded rod 72 and threaded hole 74 and their associated components. Also, this design provides a means of attaching additional components that will be discussed in greater detail below.
[0076] The present invention is also capable of being employed to finish a concrete slab that has either a ridge or valley running longitudinally though its center as illustrated in FIGS. 8 , 9 , and 10 . This is accomplished by the use of the articulation member 80 . The articulation member 80 is a self-contained device that is designed to be fitted between two screed roller members 12 . The placement of the articulation member 80 in this manner allows the connected screed roller members 12 to vary in their longitudinal axis with respect to one another thereby allowing the present invention to finish a concrete slab that contains either a central ridge or valley.
[0077] To accomplish this, a center support 82 is positioned in the desired location at the longitudinal center of the concrete forms 14 . The articulation member 80 is then positioned between two or more screed roller members 12 in a location that it corresponds in its relative location to the center support. The articulation member 80 then rides along the top of the center support 82 , the height of which relative to the concrete forms 14 , determines the rise or drop in the finished concrete's 18 surface.
[0078] The articulation member 80 contains three primary components that make this possible. The first of these is a centrally located U-joint 98 that is fixedly attached at either end to the other two components, the female and male articulation bodies, 81 and 83 . The U-joint 98 employed in this application is of a type that is commonly in automotive or other vehicle applications and allows the two screed roller members 12 to rotate around slightly different longitudinal axises.
[0079] The U-joint 98 is located in a centrally located U-joint cavity 100 of the female and male articulation bodies, 81 and 83 , which operate to tie the articulation member 80 to the screed roller members 12 . The attachment of the U-joint 98 to the female and male articulation bodies, 81 and 83 , is accomplished through the use of the rod attachment cups 102 . The rod attachment cups 102 are fixedly attached to the U-joint 98 on their inside end and fit over the end of the present threaded rod 72 on their outside. With the threaded rod 72 so positioned, an attachment pin 56 is passed through the rod attachment cups 102 and the associated threaded rods 72 .
[0080] The rod attachment cup 102 that is associated with the female articulation body 81 is also fixedly attached to an attachment cup flange 104 . The attachment cup flange 104 is then bolted to the inner surface of the female articulation body 81 by a plurality of bolts 54 . This not only fixedly attaches the U-joint 98 to the female articulation body 81 , but also serves to secure the female articulation body 81 to the associated male attachment plug 48 of the screed roller member 12 . Conversely, the male articulation body 83 is secured not only by the operation of its associated threaded rod 72 , but also by a securement bolt 76 that passes through it and engages the surface of the threaded rod 72 .
[0081] An additional component of the articulation member 80 is the pull bearing assembly 84 . The pull bearing assembly 84 is the same component of the present invention that is used on the non-powered end of a conventional screed roller member 12 that allows for the attachment of a pull rope 22 as described above. The purpose of the pull bearing assembly 84 is to provide an external surface within the screed roller member 12 which is rotationally stationary when the bulk of the screed roller member 12 is rotating during use. This is accomplished by the incorporation of an outer bearing body 90 that is isolated from the remaining components by a bearing 88 . The bearing 88 fits within a bearing cavity 89 that is machined into the outer portion of the female articulation body 81 . Finally, the outer bearing body 90 is also equipped with a pull ring 86 that allows for the attachment of an external rotationally stationary device to the screed roller member 12 .
[0082] The articulating ability of the articulation member 80 is facilitated by the methods employed to construct the female and male articulation bodies, 81 and 83 . The inner surfaces of these two components are manufactured flex gap 106 that provides room for them to longitudinally move in relation to one another. Additionally, the portion of the female and male articulation bodies, 81 and 83 , that is outside of the flex gap 106 contains a seal cavity 96 . The seal cavity 96 allows for the positioning of a seal 94 between the female and male articulation bodies, 81 and 83 . The use of the seal 94 ensures that concrete or other debris cannot enter the U-joint cavity 100 and damage the U-joint 98 contained therein. Finally, the seal 94 is isolated from the bearing 88 by the use of an isolation ring 92 .
[0083] An additional component provides the present invention with the capability of finishing wide concrete pours that is illustrated in FIGS. 11 and 12 . This is the counter rotation member 108 that, like the articulation member 80 described above, fits between and connects two sections of screed roller members 12 . Additionally, the use of the counter rotation member 108 employs the use of a center support 82 that functions in a similar manner as described above.
[0084] The counter rotation member 108 provides a means by which these two screed roller members 12 can be rotated in opposite directions during finishing operations. This is necessary in wide pours because the drive motors 24 normally employed in screeding concrete are not powerful enough to provide the rotational force to long sections of screed roller members 12 . The use of the counter rotation member 108 allows for the placement of an additional drive assembly 20 in place of the pull rope 22 thereby providing the power to finish wide concrete pours.
[0085] The counter rotation member 108 is constructed in a similar manner as described above for the articulation member 80 in that it contains a bearing 88 positioned in a bearing cavity 89 that rotationally isolates an outer bearing body 90 from the rotation of the screed roller members 12 . Additionally, the counter rotation member 108 also isolates the rotation of the two attached screed roller members 12 from one another. This is accomplished by the internal structure of the counter rotation member 108 in that its two primary components are the female and male counter rotation bodies, 110 and 112 . These two components serve to connect the counter rotation member 108 to the screed roller members 12 . Additionally, the female and male counter rotation bodies, 110 and 112 , are tied together though the internal components of the counter rotation member 108 which in turn serves to connect the entire structure.
[0086] These internal components of the counter rotation member 108 consist primarily of two related components. The first of these is the female inner flange 114 that is attached to the female counter rotation body 110 through the use of the female counter rotation attachment flange 130 and a plurality of large bolts 124 . The second is the male inner flange 116 connected to the male counter rotation body 112 through the use of a male counter rotation attachment flange 128 and a plurality of bolts 54 . The female and male inner flanges, 114 and 116 , are positioned within the counter rotation cavity 126 located within the female and male counter rotation bodies, 110 and 112 .
[0087] The female and male inner flanges, 114 and 116 , both extend from their connection to their respective component towards the center of the counter rotation cavity 126 in a manner so that the male inner flange 116 extends over approximately two thirds of the female inner flange 114 . These components are configured so that there is a space left between the inner surface of the male inner flange 116 and the outer surface of the female inner flange 114 . Additionally, the inner surface of the male inner flange 116 is equipped with a centrally positioned bearing spacer shoulder 118 and the female inner flange 114 has a corresponding bearing spacer shoulder 118 that is positioned so that an isolation bearing 120 can fit between it and the outer edge of the male inner flange's 116 bearing spacer shoulder 118 . The opposite end of the male inner flange's 116 operates to position an additional isolation bearing 120 .
[0088] The isolation bearings 120 serve to rotationally isolate the female and male inner flanges, 114 and 116 , from one another. This is accomplished not only by their positioning within the gap between the female and male inner flanges, 114 and 116 , but also by the nature of their connection to the female and male inner flanges, 114 and 116 . This manner of construction allows the female inner flange 114 and all of the components of the present invention to which it is attached to rotate in one direction while the male inner flange 116 and all of the components to which it is attached to rotate in the other thereby providing the function that is central to the counter rotation member 108 .
[0089] As stated above the female and male inner flanges, 114 and 116 , also serve to tie the female and male counter rotation bodies, 110 and 112 , together. This is accomplished by the use of securement nuts 122 , one each of which is threaded over the ends of the female and male inner flanges, 114 and 116 . The securement nut that is threaded over the open end of the female inner flange 114 tightens down on the corresponding isolation bearing 120 . This serves to force this isolation bearing 120 against the bearing spacer shoulder 118 of the male inner flange 116 which in turn forces the other isolation bearing 120 against the female inner flange's 114 bearing spacer shoulder 118 . Thus, the nature of the construction of these components of the present invention serves to rotationally tie the female and male inner flanges, 114 and 116 , together by eliminating the possibility of lateral movement when assembled.
[0090] This rotational connection is also reinforced by the use of the second securement nut 122 . When assembled, the second securement nut 122 is threaded over the open end of the male inner flange 116 and operates to force the pull bearing 88 against an additional bearing spacer shoulder 118 located on the outer surface of the male inner flange 116 . This then further restricts any lateral movement of the male inner flange 116 . Thus, the manner of construction of the counter rotation member 108 provides a means by which two connected screed roller members 12 can be rotated in opposite directions thereby allowing for the use of the present invention in the finishing of unusually wide concrete pours.
[0091] Another optional component of the present invention that adds flexibility to its operations is the center anchor member 134 and is illustrated in FIGS. 13 , 14 and 15 . The center anchor member 134 allows the present invention to finish a circular concrete pours such as those used in the construction of grain silos and other similar buildings. The center anchor member 134 provides a means by which the non-powered end of the screed roller member 12 may be properly anchored in the center of the concrete pour and rotate freely therein.
[0092] The center anchor member is made up of a stationary outer bearing ring 140 that is fixedly attached at its lower end to an anchor rod 144 and at its upper end to a handle 138 . The anchor rod 144 serves to provide the rotational aspect to the center anchor member 134 through its positioning within the anchor tube 136 that is positioned in the underlying ground at the desired location with respect to the concrete slab. The anchor tube 136 is simply an open-ended vertically oriented section of tubing that the lower end of the anchor rod 144 slips into. This method of securing the anchor rod 144 allows it to freely rotate supplying the pivotal action that is required by the operation of the center anchor member 134 . Additionally, the relative height of the anchor rod 144 in relation to the anchor tube 136 is controlled by the positioning of lock nuts 146 along the length of the anchor rod 144 .
[0093] The outer bearing ring 140 of the center anchor member 134 also provides for the pivotal attachment of the bearing 88 which in turn allows for the attachment of the screed roller member 12 . This attachment is accomplished by the use of a threaded rod 72 that is positioned so that it extends out beyond the end of the screed roller member 12 and the attached center anchor member 134 . This then allows for the placement of a centering securement nut 150 that is threaded over this extending portion of the threaded rod 72 . The centering securement nut 150 also contains a shoulder that, when installed, fills the gap between the threaded rod 72 and the center anchor member's 134 center attachment hole 148 .
[0094] The pivotal nature of the attachment of the bearing 88 within the bearing ring 140 is accomplished by a plurality of pivotal attachment bolts 142 . The pivotal attachment bolts 142 pass through the bearing ring 140 and into the outer bearing body 90 in a manner that allows pivotal motion of the outer bearing body 90 around the axis created by the pivotal attachment bolts 142 . This manner of construction allows for the altering of the angle of operation of the screed roller member 12 with relation to the center anchor member 134 providing a means by which an angled pour of the concrete can be accomplished in much the same manner as the articulation member 80 .
[0095] A still further attachment for the present invention referred to as an existing slab drop-down member 152 is illustrated in FIGS. 16 and 17 . The existing slab drop-down member 152 allows for the finishing of a concrete slab in a situation where it is desirable to construct a new concrete slab adjacent to an existing slab 154 with an upper surface that is slightly lower than that of the existing slab 154 . This application is most common in the pouring of driveways up to an existing garage.
[0096] The existing slab drop-down member 152 is employed by attaching it to the non-powered end of a screed roller member 12 . This attachment is accomplished in much the same manner as described above for other components of the present invention in that it contains an isolated bearing 88 and an outer bearing body 90 . Additionally, the bearing 88 and outer bearing body 90 are isolated from the screed roller member 12 by the use of an isolation ring 92 . Finally, the bearing 88 and outer bearing body 90 are attached to the existing slab drop-down member 152 by the use of a plurality of large bolts 124 that pass through the isolation ring 92 and the inner bearing spacer 158 and into the existing slab drop-down body 153 . This allows for the attachment of a pull rope 22 on the non-powered end of the screed roller member 12 that provides a means of controlling this end of the present invention.
[0097] The existing slab drop-down member 152 has an extending drop-down body 153 that has an outside diameter that is smaller than that of the screed roller member 12 . The drop-down body 153 allows the outer surface of the screed roller member 12 to operate at a level that is lower than the existing slab 154 thereby providing a means for finishing a concrete slab that is lower than the existing slab 154 . Thus, the use of the existing slab drop-down member 152 in conjunction with the present invention creates the desired relationship between the two adjacent concrete slabs.
[0098] A yet further attachment for the present invention is the footing member 164 and is illustrated in FIGS. 18 and 19 . The footing member 164 provides the present invention with the Figures of finishing a concrete slab that is used to form the floor of a basement where the footings 160 and walls 162 are already built. The footing member 164 is made up of a footing member body 165 that is attached to the non-powered end of a screed roller member 12 in the same manner as described for the previous attachments using an outer bearing body 90 and bearing 88 configuration.
[0099] The footing member 164 is equipped with a ring spacer 166 . The ring spacer 166 is a circular plate that is inserted between the footing member body 165 and the footing member spacer 163 in a location so that it effectively raises the screed roller member 12 up off of the footing 160 . Additionally, the footing member spacer 163 , the ring spacer 166 , and the footing member body 165 are held together by the use of a plurality of large bolts 124 . This design allows for the simplified pouring of such a concrete slab up to the wall 162 and over the footing 160 to properly construct a basement floor.
[0100] The final attachment for the present invention in terms of this discussion is the vibration compacting member 167 which is illustrated in FIGS. 20 , 21 , 22 , and 23 . The vibration compacting member 167 operates to enhance the present invention's concrete compacting effect on the unfinished concrete slab 16 . This is accomplished by the employment of a device that is commonly used in the concrete industry known as a stinger 174 . The stinger 174 is made up of a vibrating rod that is inserted into wet concrete and which drives out air pockets contained within the concrete.
[0101] In its use with the present invention, the stinger's 174 vibration drive motor 168 is attached to the drive assembly 20 . The vibration drive motor 168 has a flexible drive rod 170 that extends from it down to the stinger body 172 positioned at the drive end of the screed roller member 12 between the drive plate assembly 52 and the tube body 50 .
[0102] The attachment of the vibration compacting member 167 to the screed roller member 12 is accomplished by the use of a stinger bearing assembly 178 in a similar manner as described above for the present invention's other attachments. The stinger bearing assembly's 178 primary component is the stinger body 172 which is in turn made up of a stinger tube 173 and a stinger ring 176 . The stinger body serves to contain the stinger 174 and transfer its vibrational motion to the stinger ring 176 . The stinger ring 176 is in turn attached to the stinger bearing assembly 178 and this component transfers the vibration of the stinger 174 to the screed roller member 12 . This design serves to impart a vibrational aspect to the motion of the screed roller member 12 during the finishing operation. This vibration has been found to enhance the compacting of the unfinished concrete 16 as it operates to drive off unwanted the air pockets that are inherent in all concrete pours.
[0103] The positioning of the bearing 88 within the stinger bearing assembly 178 is accomplished by the use of the outer and inner housings, 180 and 182 . As previously stated, the stinger bearing assembly 178 is positioned between the drive plate assembly 52 and the screed roller member 12 . The inner housing 182 contains a female recess 68 and a male shoulder 70 enabling it to lock into these components. Additionally, the inner housing 182 is secured to the screed female attachment plug 46 of the screed roller member 12 by a plurality of large bolts 124 . Finally, the inner housing is constructed to have a bearing housing 184 centrally located on its outer surface. The bearing housing 184 provides a mechanism that allows the bearing 88 to be fitted within it.
[0104] The outer housing 180 provides the means for the securement of the stinger ring 176 and all of the other components attached to it. This is accomplished by the inner housing being constructed of two halves that sandwich the stinger ring 176 and outer portion of the bearing 88 . This sandwich is then held together by passing a plurality of bolts 54 through the assembled components. Additionally, when the outer housing 180 is properly positioned within the stinger bearing assembly 178 , there is a remaining rotation gap 188 left between it and the drive plate assembly 52 and the screed roller member 12 . The rotational gap 188 allows the stinger ring 176 and its related components and the bearing 88 to remain stationary while the drive plate assembly 52 and screed roller members 12 rotate. Finally, there is also a housing gap 186 left between the outer and inner housings, 180 and 182 , for the same rotational purpose.
[0105] Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein.
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A rotating cylinder cement screeding system having a drive assembly and handle at one end for powering and controlling the screeding system. The rotating cylinder is made of tubular screed rollers of varying lengths allowing a user to customize the length of the system to match a specific cement pour. Further, each tubular screed roller is supplied with a male and female end for interlocking with each other and for receiving a variety of add on attachments. The rotating cylinder may also be equipped with a constant velocity type U-joint to allow the rotating cylinder to flex and thus, allow for pours with crowns or valleys, as need by the cement installer.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a bracing structure and to a drawbar unit for a vehicle which utilizes such a bracing structure. Such drawbar units are particularly useful with construction vehicles.
2. Prior Art
The attachement of drawbars to vehicles such as heavy construction vehicles is well known. Generally, such drawbar units have been attached to the transmission case at the back of such vehicles. This has created very serious problems in that when heavy loads are being pulled by the vehicle the bolts which are holding the drawbar unit to the transmission case will often fail. Also, the transmission case itself may be ripped off or at least badly bent if the bolts themselves do not fail with the damage occurring generally adjacent the points of attachment of the bolts to the transmission case. Still another problem with prior art drawbar units has been that they tend to be relatively bulky and also relatively difficult and time consuming to fasten in place and remove. Still further, the prior art drawbar units have tended to extend a relatively great distance rearwardly of the main frame of the vehicle carrying them. This has created problems of relatively large moments being created which cause relatively large stresses at the points of attachment of the drawbar unit to the vehicle.
SUMMARY OF THE INVENTION
The present invention is directed to overcoming one or more of the problems as set forth above.
According to the present invention there is provided a bracing structure for supporting an article generally centrally intermediate and extending longitudinally away from the first ends of a pair of generally parallel spaced apart members. The bracing structure comprises a pair of generally Z-shaped brace means, each having a first leg thereof affixed to the article, a second leg thereof affixed to a respective one of the members and a bridge from generally a first end of the first leg, said first end of said first leg being longitudinally removed from the first ends of the members towards the second ends thereof to generally a second end of the second leg, said second end of said second leg being longitudinally intermediate the first end of the first leg and the first ends of the members.
The bracing structure of the present invention is intended to provide the strength attainable with a conventional box-beam structure and to further afford greater convenience in providing accessibility to the fastener members used in connecting the bracing structure to adjacent componentry.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood by reference to the figures of the drawings wherein like numbers denote like parts throughout and wherein:
FIG. 1 illustrates in top view, partially cut away, a drawbar unit in accordance with the present invention;
FIG. 2 illustrates a view taken along the line II--II of FIG. 1; and
FIG. 3 illustrates a view taken along the line III--III of FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Adverting now to the figures of the drawings there is illustrated therein a vehicle, part of which is shown very generally at 10 and which comprises a pair of generally vertical frame members 12, 12', one extending along each side 14, 14' of the vehicle 10 to a rearward end 16 thereof. The present invention relates most particularly to a drawbar unit 18 which is particularly useful in such a structural environment.
A hitch 20 is supported generally centrally intermediate the frame members 12, 12' and adjacent the rearward end 16 of the vehicle 10. In accordance with the present invention the pair of generally Z-shaped brace means 22, 22' serve to supportingly hold the hitch 20 in place. Each of the Z-shaped brace means 22, 22' have a first leg 24, 24' thereof supportingly and generally removably securingly affixed to the hitch 20. A second leg 26, 26' of the Z-shaped brace means 22, 22' respectively is affixed to a respective one of the frame members 12, 12'. A respective bridge 28, 28' extends from generally a forward end 30, 30' of the respective first leg 24, 24' to generally a rearward end 32, 32' of the respective second leg 26, 26'. The aforementioned structures thus define the basis of the bracing structure of the present invention.
Generally, there are a pair of generally coaxially aligned aperture means 34, 34', one of which is seen in FIG. 1 in cut away view, one of said aperture means 34, 34' passing generally horizontally through each of the respective frame members 12, 12' adjacent the rearward end 16 of the vehicle 10. The frame means 12, 12' are generally reinforced via reinforcing means 36, 36' so as to extend somewhat the length of the respective aperture means 34, 34' and to thereby provide overall strength at the points of affixation of the Z-shaped brace means 22, 22' to the respective frame members 12, 12'. Similarly, the respective second legs 26, 26' of the Z-shaped brace means 22, 22' are generally reinforced by reinforcing means as illustrated at 38, 38' to again provide additional strength at the area of attachment of the respective second legs 26, 26' to the respective frame members 12, 12'.
To provide extra rigidity to the drawbar unit 18, a pair of upper generally horizontal plates 40, 40' are integrally affixed, one to a top 42, 42' of each of the respective brace means 22, 22'. Also, a pair of lower generally horizontal plates 44, 44' are integrally affixed to a respective bottom 46, 46' of each of the brace means 22, 22'. Thus, a box like support is provided with the bridges 28, 28' of the Z-shaped brace means 22, 22' providing significant rigidity thereto. Also, the area from the respective rearward end, 32, 32' of the respective second legs 26, 26' to a respective rearward end 48, 48' of the respective first leg 24, 24' is open thus allowing easy access to the means which secure the hitch 20 to the respective first legs 24, 24' of the respective Z-shaped brace means 22, 22'. In the embodiment illustrated it is clear that nut and bolt means 50 serve to removably secure the hitch 20 to the respective first legs 24, 24' of the Z-shaped brace means 22, 22'.
A pair of pin means 52, 52' serve for affixing each respective one of the members 12, 12' to a respective one of the second legs 26, 26'. Thus, the pins 52, 52' are seen to be held in bores within the respective support structures 36, 36' and 38, 38' associated respectively with the respective frame 12, 12' and the respective second leg 26, 26'.
It is desirable to provide a pair of generally vertical walls 54, 54', one integrally affixed to each of the Z-shaped brace means 22, 22' adjacent to and generally parallel to second legs 26, 26' thereof and on an opposite side of each respective one of said frame members 12, 12' from said respective second legs 26, 26' of said Z-shaped brace means 22, 22'. When such vertical walls 54, 54' are provided, respective wall hole means 56, 56' are generally provided one passing generally through each of the walls 54, 54' in coaxial alignment with the respective aperture means 34, 34'.
The drawbar unit 18 of the present invention can be advantageously made still more rigid by provision of a pair of first stiffener plate means 58, 58', one affixed between an intermediate portion 60, 60' of each respective one of the first legs 24, 24' and each respective one of the bridges 28, 28'. Further, the drawbar unit 18 can be made more rigid still by the provision of a pair of second stiffener plate means 62, 62', one affixed between each respective one of the generally vertical walls 54, 54' and each respective one of the bridges 28, 28'. It may be necessary to use as the stiffener plate 62, 62', a pair of plates which will not interfere with any portion of the frames 12, 12'. Curved second stiffener plate 62, 62' are illustrated in the figures of the drawings.
The drawbar unit 18 is preferably provided with means for preventing pivoting thereof so that the hitch 20 is substantially prevented from vertical movement. Thus a pair of pivot preventing means 64, 64' are provided which accomplish this purpose. Briefly, the pivot preventing means 64, 64' comprise nut and bolt means 66, 66' which pass through appropriate bores in both frame members 12, 12' and the respective second legs 26, 26' of the Z-shaped brace means 22, 22'. Generally, an additional bore is provided through the vertical walls 54, 54' when such are present. The bores through the respective second legs 26, 26', frame members 12, 12' and vertical walls 54, 54' generally provide a relatively loose fit as illustrated at 68' in FIG. 1. A symmetrical construction exists at the opposite side of the vehicle, although it is not specifically illustrated for convenience and clarity. At the same time, the fit about the respective pin 52, 52' is relatively tight whereby the great majority of forces transmitted from the drawbar unit 18 to the frame 12, 12' proceeds via the respective pins 52, 52' . This serves to prevent shearing of the nut and bolt means 66, 66' while still assuring that they are present to resist any rotating motion in a vertical plain by the hitch.
The hitch 20 is preferably such that it can be adjusted for two different heights above the ground upon which the vehicle 10 is sitting. This can be advantageous in assuring that loads of at least two different heights can be pulled substantially directly forwardly by the vehicle 10. Adverting particularly to FIG. 2 it will be seen that the hitch 20 to accomplish this purpose can be formed of a first portion 67 which is affixed to the first legs 24, 24' by the nut and bolt means 50. Also, the hitch 20 comprises a second portion 68 which is vertically displaced from the first portion 67 with the second portion 68 comprising follower vehicle engaging means such as a post 70 as illustrated. It is clear then that the hitch 20 can be connected as illustrated in FIG. 2 or that alternatively, the hitch 20 can be mounted with the second portion 68 thereof vertically displaced downwardly from the first portion 67 thereof thus providing a second and lower position for the post 70.
It is very desirable that the hitch 20 be as close as reasonably possible to the vehicle 10 to reduce moments created between these structures. Thus, it is desirable that the follower engaging means, in the embodiment illustrated the post 70, extends rearwardly from the rearward end 72, 72' of the frame members 12, 12' a distance of generally no more than about one and one-half times the longitudinal extension from the forward end 30, 30' of the respective of the first legs 24, 24' to the respective rearward ends 48, 48' thereof.
It is preferred that a pair of back-up pivot preventing means, one of which, 74, is illustrated in FIGS. 1 and 2, be provided for preventing each of the second legs 26, 26' respectively from pivoting about affixation thereof to a respective one of the members 12, 12'. Such back-up pivot preventing means 74 operate only when the pair of pivot preventing means 64, 64' either fail or are absent. In the particular embodiment illustrated, the back-up pivot preventing means 74 comprises a ridge 76 formed by a cut out in the upper plate 40. Should forces tend to rotate the hitch 20 about the pins 52, 52' thus tending to rotate the respective second arms 26, 26' about the respective pins 52, 52', and should the pair of nut and bolt means 66, 66' be absent, then the ridge 76 will contact the top of the frame member 22 to prevent pitching which corresponds to the hitch 20 rotating in a clockwise direction. Similarly, the back-up pivot preventing means 74 includes means for preventing pitching corresponding to a counterclockwise movement of the hitch 20. In the particular embodiment illustrated, a portion 78 of the lower plates 44, 44' extends beneath the respective frame members 12, 12' and contacts the bottoms of the respective frame members 12, 12' on attempted counterclockwise rotation of the hitch 20 about the pin means 52, 52'.
It will be seen that the bracing structure, generally the drawbar unit 18 of the present invention, provides very rigid support while still allowing very easy access to the bolt means 50 for the changing of hitches. Further, in utilizing a structure in accordance with the present invention it is possible to operate with the hitch 20 relatively near the rearward end 16 of the vehicle 10. Further, it is a very important feature of the present invention that the drawbar unit 18 is supported by the frame members 12, 12' and is not supported by connection to the transmission case of the vehicle 10.
While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modificaton, and this application is intended to cover any variations, uses or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as fall within the scope of the invention and the limits of the appended claims.
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A heavy duty drawbar features a Z-type brace which is accessible from the end of a vehicle which carries the drawbar. The Z-type brace provides significant strength for the overall drawbar while still allowing easy access to the hitch fastening bolts for easy changing. Also, the hitch can be placed very close to the vehicle when held by such a Z-type brace. Two of the Z-type braces are supported each between generally vertical frame members and the hitch of the drawbar is supported between the two Z-type braces.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation-in-Part of my prior applications, namely AIR PROPULSION APPARATUS WITH WINDMILL HAVING MULTIPLE WINDMILL BLADES TO ENHANCE PERFORMANCE, Ser. No. 10/026,334, filed Dec. 21, 2001 now abandoned and the disclosures of the applications cross referenced therein, namely, AIR PROPULSION DEVICES, Ser. No. 60/258,957, filed Dec. 29, 2000; WINDMILL WITH MULTIPLE DOUBLE-ACTING PISTON/CYLINDER COMPRESSOR SYSTEM AND APPARATUS AND METHOD OF MOUNTING MULTIPLE WINDMILL BLADES TO ENHANCE PERFORMANCE, Ser. No. 09/990,855, filed Nov. 21, 2001 now abandoned; and includes the applications referenced therein, namely, WINDMILL WITH TWO PISTON COMPRESSOR SYSTEM, Ser. No. 60/252,772, filed Nov. 22, 2000; and APPARATUS AND METHOD OF MOUNTING MULTIPLE BLADES TO ENHANCE PERFORMANCE, Ser. No. 60/252,812, filed Nov. 22, 2000; the disclosures of all of which are incorporated herein by reference as if fully set forth.
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to improvements in devices powered by air, and more particularly, to windmills and apparatuses connected to them, such as, vehicles propelled by motor driven propellers, augmented by a windmill; which apparatuses may additionally have multiple airfoils in a stack to enhance power output, lift and propulsion.
2. Background Art
In the prior art, it was known to use windmills to compress and store compressed air. Such a system is shown in my prior art U.S. Pat. No. 6,132,181, issued Oct. 17, 2000, which discloses windmill structures and systems. Therein I disclose a number of ways of attaching the rotating shaft of a windmill to various mechanical means and compressors.
In the prior art, it is known to use air to power vehicles such as automobiles. Despite extensive knowledge of the desirability of such vehicles, there is not currently on the market for mass production and delivery to the general public any such device. Guy Negre, a French engineer, allegedly has several patents and has produced a number of prototypes. Reportedly, air would be stored in a carbon-fiber or fiberglass tank at very high pressure (4,351 pounds per square inch), then combined with warmer outside air in a cylinder to move a piston. It may be that the car would actually scrub the ambient air with an onboard carbon filter.
It is reported that around 1900, compressed air trams plied the streets of Paris. Reportedly, the trams made only short trips. Attempts to run cars or trucks on compressed air have foundered on the weight of the air tanks needed to obtain a minimally acceptable range of 100 miles or more.
Engineers who have looked at hybrid-powered vehicles have felt that compressed air compared unfavorably with batteries as a medium for storing energy and were inherently inefficient. It is noteworthy that the environmentalists feel that the car, rather than being pollution-free, would only be as clean to the environment as the plants that produce the electricity used in compressing the air to drive the vehicles. To that end, the proponents of compressed air vehicles state that environmentally complete clean hydro power or solar panels could be used to supply the electricity.
One of the problems that I have noted in my work with windmills is that there may be periods when the wind is either very slow or very fast for a sustained period of time. This can affect the usefulness of the windmill system in compressing and storing compressed air.
Further, in the prior art, it has been known to mount air foils in stacks, such as the wing arrangement in bi-planes and tri-planes. I have discovered that the performance of such arrangements may be enhanced depending on the mounting and relative positioning of the air foils.
DISCLOSURE OF THE INVENTION
Summary of the Invention
I have invented means and methods for enhancing the performance of windmills and the devices connected to them. By enhancing, I mean making that performance greater than it otherwise would have been but for my invention.
I disclose hereinafter performance results to illustrate this statement.
Examples include, without limitation, mounting multiple blades, interconnecting the blades and using multiple windmills, such as in vehicles.
More particularly, I have invented an aerodynamic air foil structure and method which is useful not only for wind design arrangements, but also for air foil blades in other devices, such as fans and windmills.
This is an improved airfoil arrangement which can provide airfoils in combination which provides needed structural strength while causing (windmill) lift; (propeller) thrust; (fan) flow enhancement which is greater than the sum of the individual air flows (in the same air flow conditions).
I have invented an air propelled vehicle with a windmill system which utilizes an improved airfoil arrangement comprising airfoils in combination which provide needed structural strength while causing windmill air flow enhancement which is greater than the sum of the individual air flows (under the same air flow conditions).
In a preferred embodiment, multiple pairs of blades are attached to multiple hubs on a windmill shaft. The blades in each pair of windmill blades are interconnected with braces.
My invention comprises, as well, an air propelled vehicle, comprising: an air propulsion means to propel said vehicle; said air propulsion means having a source of power, such as a motor, to drive the air propulsion means; a power transfer means, such as a shaft, engaging said source of power; and a first clutch means for engaging said power transfer means in a selected condition; a windmill means to provide enhanced propulsion to said vehicle when engaging said first clutch means in said selected condition. The vehicle described above further comprises a second clutch means coacting with said source of power to disengage said source of power from driving said propulsion means when said windmill means provides propulsion which exceeds that of the source of power. In one embodiment the air propulsion means comprises a propeller. In another embodiment, the air propulsion means comprises two propellers.
I have invented a windmill compressed air system which utilizes two double acting pistons and cylinders. These are most preferably of different volume, but have the same stroke length. They have pressure control valves to provide for alternative choices depending on wind availability. The larger diameter piston is used to quickly pump up the volume of the storage tank for the compressed air to a desired level. After that, the smaller diameter piston takes over.
The larger diameter piston cuts off at lower air speeds, so that at least some useful work can be gained from the windmill turning and driving the smaller diameter piston.
Further, the improved airfoil arrangement comprises airfoils in combination which provide needed structural strength while causing windmill air flow enhancement which is greater than the sum of the individual air flows (under the same air flow conditions).
I have invented a windmill compressor apparatus comprising:
windmill means mounted to a windmill shaft to rotate said shaft in response to air flow through said windmill means; multiple double-acting piston/cylinder means each having a piston operating within a cylinder to compress air upon movement of the piston within the cylinder; each of said cylinders having a piston shaft connected to said piston therein; said piston shaft extending from said cylinder; drive means connecting said piston shafts to said windmill shaft to drive said piston shafts in response to rotation of said windmill shaft; and conduit means connected to the piston/cylinder means to permit the flow of air into said cylinders to receive compressed air from said cylinders.
I have further invented a windmill compressor apparatus in which I position the multiple double-acting piston/cylinder means such that the cylinders are radially space from one another.
Most preferably, the cylinders are of different diameters. Pressure relief valves are disposed in discharge lines exiting said cylinders of different diameters. The pressure relief valve for the cylinder with the largest diameter is set to be actuated at a pressure which is less than the pressure relief valve for the cylinder with the smaller diameter.
The drive means comprises a crank arm attached to the windmill shaft to rotate therewith; said crank arm having a portion thereof connected to the piston shafts to rotate said piston shafts, thereby withdrawing and inserting the shafts with respect to the cylinders to compress air. The crank arm has a portion thereof opposite to the end which is connected to the piston shafts, which portion acts as a counterbalance to the pistons.
The windmill compressor apparatus as defined above may further comprise multiple pairs of windmill blades. The multiple pairs of blades are attached to multiple plates on a hub on said windmill shaft.
The blades in each pair of windmill blades are interconnected with braces.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a schematic representation of a plurality of air foils taken in end of view and arranged in a stack;
FIG. 2 shows a plurality of blades mounted to the hub of a windmill directly connected to a motor and being arranged in a stack;
FIG. 3 shows a plurality of blades mounted on a hub;
FIG. 4 shows is an end view of a stack of blades connected together and mounted to a hub;
FIG. 5 shows further details of mounting blades, such as those shown in FIG. 4 ;
FIG. 6 shows the details of mounting a blade to a hub;
FIG. 7 shows the details of a mounting of a blade to a hub;
FIG. 8 shows the details of a blade with stiffeners;
FIG. 9 shows an alternate detail of structural parts;
FIG. 10 shows comparative test results for several airfoils and bi-vane airfoil in accordance with one embodiment of my invention;
FIG. 11 shows performance curves for a windmill air compressor in accordance with one embodiment of my invention;
FIG. 12 is a schematic side view of the vehicle in accordance with one embodiment of my invention;
FIG. 13 is a schematic side view of the vehicle in accordance with one embodiment of my invention;
FIG. 14 is a rear view of a windmill system;
FIG. 15 is a side view of the windmill system shown in FIG. 14 ; and
FIG. 16 is a top view of a portion of the windmill system shown in FIG. 15 ;
FIG. 17 is a view similar to FIG. 2 showing multiple sets of three blades mounted on a single hub; and
FIG. 18 is an enlarged view of a modified portion of FIG. 15 showing a set of three blades mounted on a single hub as part of a windmill apparatus.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , this shows graphically an end view representation of a plurality of air foils or blades positioned with respect to one another and the entry air flow, as shown by the arrow “A”. The blades are shown as being predominantly flat, of uniform cross-section and having a lip at the down wind edge (as shown in my prior U.S. patents for air foils and windmill structures such as U.S. Pat. No. 6,132,181, issued Oct. 17, 2000). The blade 10 has a cord length “X” measured from the leading edge tip 12 to tip 14 on a line parallel to the plane of the central portion 16 . Blade 18 is most preferably somewhat smaller in overall length. The blades are positioned with respect to one another such that the center 20 of the central portion 16 of the blade 10 is spaced approximately 50% of the blade cord length “X”, that is, X divided by 2, from the center 20 to the center 22 of the central portion of the blade 18 .
The lower blade 18 is positioned with respect to the upper blade 10 with a 15 degree increased angle of attack greater than the angle of attack of the upper blade 10 .
I discovered that this arrangement provides for more air flow deflected in a downward direction. Tip 24 of the blade 18 is positioned approximately 1/10th of the cord length “X” back from the tip 14 on a line taking perpendicular to the line parallel to the cord length “X”; said line passing through the tip 14 as illustrated in FIG. 1 .
The cord length of the blade 18 is approximately 70% of “X”.
In an alternate embodiment, a third blade 26 can be positioned if it is dimensioned and positioned with the same ratios as given with respect to blades 10 and 18 .
FIG. 2 shows how two of these blades 110 and 112 might be held together by stand-offs and bolts designated generally 114 and then mounted to a hub 30 of a windmill by three bolts designated generally 116 fastened through one of the blades. The hub is a plate fixed to the shaft 118 of the windmill; which in turn is connected to the load 120 .
FIG. 3 shows a preferred method of mounting windmill blades to a hub. In this Figure, the blades 210 are offset from the center, as clearly illustrated by the center line CL of the windmill shaft 230 and the centerline BCCL of the blade chord.
FIG. 4 shows the method of mounting the blades with respect to one another and with respect to the hub of a bi-blade windmill. This is an alternate arrangement of blades and specific dimensions provided were used for experimental purposes. Herein the blades 32 and 34 are spaced from one another and held in position by threaded stand-offs 36 and 38 . The blades are shown in greater detail in FIG. 5 .
FIGS. 6 and 7 show details of the mounting at the ends of the blades to the hub plates 40 , 42 . In these arrangements, additional braces 44 , 46 are provided for the purposes of stiffening.
Additional stiffening arrangements are provided by a plurality of stiffening members 48 , FIG. 8 . Alternatively, the stiffening members may be staggered, as shown generally at 50 in FIG. 9 .
In an alternate embodiment, if one were to mount blades to a hub in an offset fashion, they can be overlapped and canted.
FIG. 10 shows comparative test results for several airfoils and bi-vane airfoil in accordance with one embodiment of my invention.
FIG. 11 shows performance curves for a windmill air compressor in accordance with one embodiment of my invention.
FIG. 12 shows schematically a vehicle designated generally 100 , such as, for example, a truck or car, which is propelled by an apparatus comprised of an engine, shown schematically at 102 , in combination with a propeller, shown schematically at 104 . The engine is fixedly attached to the frame 106 of the vehicle 100 in any suitable way, such as by means of the support structure 108 . The device is designed such that when the engine is operating, it rotates the shaft 110 which in turn rotates the propeller 104 , causing thrust to drive or propel the vehicle. Outboard of the engine and propeller apparatus, I have provided a windmill system apparatus which comprises a windmill designated generally 101 having a plurality of blades 1112 mounted to a hubs 114 and 115 connected to the shaft 110 (preferably through a clutch means 102 ) which is journaled in bearings 118 a and 118 b mounted on beams 201 a and 201 b which are rigidly connected to the frame 106 supporting the entire structure.
A plurality of air foils or blades 1112 are positioned radially with respect to one another. Each of the blades shown are predominantly flat, of uniform cross-section and have a lip at the downwind edge (as shown in my prior U.S. patents for air foils and windmill structures such as U.S. Pat. No. 6,132,181, issued Oct. 17, 2000). The blades are positioned with respect to one another such that the center of the central portion of one blade is spaced approximately 50% of the blade cord length from the center to the center of the central portion of the other blade.
I discovered that this arrangement provides for more air flow deflected in a downward direction.
In this arrangement, additional braces 117 and 119 may be provided for the purposes of stiffening.
A plurality of such blade arrangements are provided spaced radially from one another.
The outboard end of the shaft 110 may be connected for rotation to an additional propeller 112 to provide further thrust.
The windmill 101 engages the shaft 110 through a clutch means 102 , which functions as follows: as long as the windmill is slower than the shaft 110 being driven by the propeller 104 , it overrides the windmill and allows the propeller to turn without engaging the windmill. When the windmill 101 goes faster than the shaft 110 , the clutch engages and the windmill assists in driving the power transfer means, that is, the shaft 110 . A second clutch 140 disengages the source of power, that is, the motor and overrides it when there is enough power supplied by the windmill for vehicle propulsion, that is, the motor power source is cut off.
Once the aerodynamic lift of the windmill is input into the system, it is theorized that the system is getting energy from atmospheric pressure due to gravity.
It is also theorized that the optimum vehicle speed will be between 30 and 45 mph depending on the efficiency of the airfoil design in the windmill. The power available from the windmill ultimately exceeds the power required to move the vehicle. Prior to that speed, the windmill assists in powering the vehicle. This embodiment of my invention is further illustrated in FIG. 13 which shows a three wheel vehicle 1000 . The windmill 1002 is geared up to apply continuous farce as the speed of the vehicle increases. This must be a calculated ratio as to windmill power profile (speed) to tire size.
Herein, an engine to wheel clutch is needed, but a windmill clutch drive is not necessary. As vehicle speed increases, the engine powers the vehicle with increasing windmill assist up to the power required and power available solely from the windmill. The intersect speed is perhaps in the 40 to 60 mph range. At that point, the windmill runs the vehicle.
Windmill placement in front of the vehicle causes some vehicle drag shading by work extraction, slowing air flow just forward of the vehicle. Vehicle drag is intercepted to do windmill work. Enhancement is provided in that aerodynamic power via windmill has an eight times power increase available from wind vehicle speed increases. Drag has a lower exponential increase from work derived from aerodynamic lift (rotational torque) provided from windmill blades.
In the most preferred embodiment, I use multiple airfoils as shown in this and my prior applications noted above.
In a further embodiment of my invention, the additional propeller 112 is used to propel the vehicle.
This device draws power from atmospheric pressure and/or motion by gravity and wind and vehicle motion done by ordinary means to assist and ultimately take over vehicle propulsion driving power. It employs a windmill as supplementary drive power to a gas, electric, diesel or compressed air, or the like, source of primary power. This inputs partial and perhaps full takeover of the drive power after reaching the speed that makes possible over 100% of the propulsion power requirement.
In its optimum condition, the windmill power input may reach self-sustaining drive power. That is, it could provide all of the power input necessary to propel the vehicle.
It is theorized that the basis for this aerodynamic lift comes from gravity as an amplification of various inertial bases. Therefore, there is in some speed range less drag in making power than in using power.
Referring to FIGS. 14-16 , and 18 they show a windmill system apparatus which comprises a windmill designated generally 1000 having a plurality of blades 1200 , 1202 and 1204 mounted to plates 1400 , 1500 and 1550 connected to a hub 1575 connected to a shaft 1600 which is journaled in bearings 1800 mounted on a horizontal beam 2000 which is rigidly connected to a vertical tube 2200 and a base 2400 supporting the entire structure.
Referring to FIG. 15 , this shows a side view of a plurality of air foils or blades 1200 positioned with respect to one another. The blades are shown as being predominantly flat, of uniform cross-section and having a lip at the down wind edge (as shown in my prior U.S. patents for air foils and windmill structures such as U.S. Pat. No. 6,132,181, issued Oct. 17, 2000). The blades are positioned with respect to one another such that the center of the central portion of one blade is spaced approximately 50% of the blade cord length from the center to the center of the central portion of the other blade.
I discovered that this arrangement provides for more air flow deflected in a downward direction.
FIG. 15 shows the mounting at the ends of the blades to the hub plates 1400 and 1500 . In this arrangement, additional braces 1700 and 1900 may be provided for the purposes of stiffening.
See for example FIG. 17 which shows multiple sets of three blades 110 , 111 and 112 mounted to a single hub 30 .
A plurality of such blade arrangements are provided spaced radially from one another.
The outboard end of the shaft 1600 is connected for rotation to a crank arm 2800 . One end 2900 of the crank arm 2800 is “T” shaped and is used to counterbalance the stroke of the pistons in the piston/cylinders 4200 , 4400 . The other end 3000 of the crank arm has a shaft 3200 extending therefrom which supports bearings 3400 and 3600 . Mounting means disposed about these bearings support and are connected respectively to the piston shafts 3800 and 4000 of the dual acting piston/cylinders 4200 and 4400 , respectively. The other ends of the air cylinders are mounted to be pivoted on bases 4600 and 4800 , respectively.
In operation, as the windmill rotates, it turns the shaft 16 which, in turn, rotates the crank arm 2800 . Since the shafts 3800 and 4000 of the pistons are journaled to the shaft 3200 , as the crank arm rotates, it drives the pistons in and out of their respective cylinders. One of these cylinders of the piston/cylinder 4400 is of a greater diameter than the other, 4200 . Both of the cylinders are double acting and both have the same stroke length on rotation of the crank arm. However, they are spaced radially so as to sequence top and bottom dead center points (by approximately 30 degrees), thereby distributing the loading over a longer duration of rotation and reducing the maximum force needed for a given pounds per square inch/cubic feet per minute rate.
Referring to the Figures, they show the air exchange system using these two piston/cylinders.
Since there are check valves at each end of the cylinders, each cylinder is double acting in that on the withdrawal stroke of the piston shafts 3800 , 4000 , compressed air is forced out of the upper end of the cylinders of the piston/cylinders 4200 , 4400 in FIG. 16 ; and on the down stroke, compressed air is forced out of the lower end of the cylinders. There are check valves 5000 , 5200 , FIG. 15 , at both ends to keep the air from flowing back in once it has been exhausted from the cylinder. There are also check valves 5400 , 5600 , FIG. 15 , at the air intake to keep the air from flowing out once it has been drawn into the cylinder. Down stream of the exhaust check valves, such as 5000 and 5200 , there are adjustment relief valves 5700 , 5900 which will be discussed more fully hereinafter. Also, downstream of the check valves are check valves 5800 ; to keep air from flowing back into the system. Downstream from that valve 5800 , there is a hose or piping 6000 to the compressed air reservoir tank 6200 . The same piping system is provided for both cylinders.
System Operation
In operation, the pressure relief valves 5700 , 5900 are set at predetermined pressures. For example, for the bigger diameter cylinder 4400 ; relief valve 5700 might be set at 55 or 60 pounds per square inch. For the smaller diameter cylinder, pressure relief valve 5900 might be set at approximately 86 pounds per square inch pressure. Thus, after the pressure reaches 55 psi, the valve 5700 simply exhausts its compressed air. Therefore, the windmill does not have to push against the combined forces of the bigger and smaller piston/cylinders. Once that pressure is reached, the smaller piston/cylinder nevertheless keeps working and keeps compressing air up to its limit of approximately 86 pounds.
The smaller cylinder is designed to work with winds of approximately 6 to 10 mph. Once the volume is reached in the tank 6200 and the lower pressure limit is reached, the bigger diameter cylinder drops out of the production of compressed air, so that at least something is gained from the windmill system. Otherwise, the windmill would stall because it cannot drive both pistons at low speeds. Thus, this arrangement extends the range of useful work that the windmill can perform.
Note that when no pressure is in the tank 6200 and the windmill first starts up, both cylinders pump compressed air into the storage tank as pressure in the tank climbs to the preset pressure of the larger cylinder.
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A windmill apparatus has multiple pairs of blades to enhance power output and lift performance. The apparatus has multiple double acting piston/cylinders actuated by the windmill, which includes several clutches that are used to engage and disengage the windmill from the motor.
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This application is a national phase of International Application No. PCT/US2003/027059, filed Aug. 29, 2003, which was published in English as International Publication No. WO 2004/022846 and claims the benefit of U.S. Provisional Application No. 60/408,251, filed Sep. 4, 2002.
BACKGROUND OF THE INVENTION
With the rising cost of wood and the shortage of mature trees, there is a present need to find good quality substitutes for wood which will continue long into the future. Additionally, good quality wood substitutes are more durable and longer-lasting than wood since they are less susceptible to termite destruction and wood rot.
Over the past several years a growing market has emerged for the use of polymer-wood composites to replace traditional solid wood products in applications such as decking, windows, fencing, automobile interiors and pallets. Polymer-wood composites contain from about 30 to about 80 percent cellulosic fibers. Cellulosic fibers act as filler or reinforcement in the polymer-wood composites. One key to achieving a high quality polymer-wood composite is a thorough dispersion of cellulosic fiber in the polymer matrix. To achieve this, many leading producers of polyethylene-wood decking have found lubricants to be essential.
Polymer-wood composites containing higher concentrations of cellulosic fibers are more susceptible to attack by fungi. Therefore, a present need exists for a compound which can function not only as a lubricant but also as an antimicrobial. Such a compound should lower the cost, simplify the manufacturing process and achieve high quality polymer-wood products with better appearance, dimensional stability and decay resistance.
BRIEF SUMMARY OF THE INVENTION
This invention is directed to an extrudable and extruded polymer-cellulosic fiber composite comprising a polymer, e.g., high density polyethylene (HDPE), cellulosic fiber and a quaternary ammonium alkyl salt. Certain of these quaternary ammonium alkyl salt are new compositions of matter.
A further embodiment of the invention is a method of preventing decay of a polymer-wood composite comprising mixing a quaternary ammonium alkyl salt into an extrudable composition containing a polymer and cellulosic fibers before performing an extrusion process on the extrudable composition.
DETAILED DESCRIPTION OF THE INVENTION
It has been discovered that quaternary ammonium alkyl salts act as both a lubricant and a fungicide in the polymer-cellulosic composites.
The quaternary ammonium alkyl salts have the following general formula:
wherein X is an alkane carboxylate O—C(O)R, alkyl sulfate OS(O) 2 OR, alkanesulfonate OS(O) 2 R, alkyl phosphate OP(O)(OH)OR—, (O-)alkyl phosphonate OP(O)(H)—OR; R is an alkyl group having from 8 to 22 carbon atoms, and R 1 is a long chain alkyl group or a benzyl group and,
where the R 1 group is a long chain alkyl group, R 2 and R 3 are short chain alkyl groups and R 4 is a short or long chain alkyl group and, where R 1 is a benzyl group, R 2 is a short chain alkyl group and R 3 and R 4 are each either short or long chain alkyl groups. The aforesaid long chain alkyl groups have from 8 to 22 carbon atoms, preferably from 10 to 18, and the short chain alkyl groups have from 1 to 4 carbon atoms, preferably 1 or 2.
Examples of the quaternary ammonium cation in the quaternary ammoniumalkyl salts include, but are not limited to, alkyldimethylbenzylammonium in which the alkyl group contains 1-25 carbon atoms, didecyldimethylammonium, alkyltrimethylammonium, octyldecyldimethylammonium, dioctyldimethylammonium, didecylmethylpropylammonium, didecylmethylbutylammonium, benzylhexadecyldimethylammonium, didecylmethyl-4-chlorobenzylammonium, didecylmethyl-3,4-dichlorobenzylammonium, decyloctyldimethylammonium, decyloctylbenzylmethylammonium, decyldodecyldimethylammonium, decyldodecylethylmethylammonium, dodecylbenzyldimethylammonium, tetradecylbenzyldimethylammonium, diundecyldimethylammonium, dinonylhydroxyethylmethylammonium, didecylhydroxypropylmethylammonium, and diundecyldihydroxyethylammonium, and combinations thereof. Blends of compounds containing dioctyl, didodecyl and decyloctyl compounds or didecyl, didodecyl and decyldodecyl compounds may also be used. These cations can be combined with any of the anions, that is, those represented by X in the above formula. Preferred quaternary ammonium alkyl salts are alkyldimethylbenzylammonium lauryl sulfate (Barquat LS) and didecyldimethylammonium lauryl sulfate (DDA-LS) and the corresponding alkyl carboxylate. The sulfonate, phosphate, and phosphite salts of the quaternary ammonium alkyl salts are also of interest. These are new compositions of matter.
A preferred quaternary ammonium lauryl sulfate is an alkyldimethylbenzyl ammonium lauryl sulfate containing an allyl group containing 8 to 22 carbon atoms. Alkyldimethylbenzyl ammonium lauryl sulfate may be made by processes known to those skilled in the art. An alkyldimethylbenzyl ammonium chloride may be reacted with sodium lauryl sulfate in water at a temperature of about 60° C. A white precipitate of alkyldimethylbenzyl ammonium lauryl sulfate is formed after about half an hour. The reaction is as follows:
wherein R is a C 1 -C 25 alkyl group, preferably a C 10 -C 12 group.
The reaction temperature ranges from 20° to 140° C., preferably 60° C. The molar ratio of alkyldimethylbenzyl ammonium chloride to sodium lauryl sulfate ranges from about 1:3 to about 3:1, preferably about 1:1. The solvent may be water or an organic solvent. If the reaction takes place in an organic solvent, sodium chloride is precipitated and the quaternary ammonium lauryl sulfate remains in solution. The organic solvent may be, for example, lower alcohols, acetone and dichloromethane. The quaternary ammonium lauryl sulfate is collected after the organic solvent evaporates off.
The polymers used in the polymer-wood composition are virgin polymers which include, but are not limited to, polyolefins and polyvinyl compounds, as for example, HDPE, LDPE, LLDPE, UHMWPE, polypropylene (homo- and copolymer), PVC, and combinations thereof. A preferred polyolefin is HDPE, available as a “barefoot” (no additives) reactor from powder (Equistar® LB100-00) having a 0.4 Melt Index (MI). This polyolefin is a product from Equistar Chemicals LP of Houston, Tex.
The extrudable and extruded polymer-cellulosic fiber composites of the present invention contain the ingredients in the following Table 1 (weight percentages are based on the weight of the total composition):
TABLE 1
Ingredients
Amount
Preferred Amount
Polymer
About 30 to 70 wt. %
About 40 to 60 wt. %
Cellulosic Fiber
About 70 to 30 wt. %
About 60 to 40 wt. %
Quaternary ammonium
About 1 to 7 phc
About 2 to 5 phc
alkyl salt
A wide variety of cellulosic fibers can be employed in the composite of the present invention. Illustrative cellulosic fibers include, but are not limited to, wood and wood products, such as wood pulp fibers; agricultural wastes such as non-woody paper-making fibers from cotton; from straws and grasses, such as rice and esparto; from canes and reeds, such as bagasse; from bamboos; from stalks with bast fibers, such as jute, flax, kenaf, cannabis, linen and ramie; from leaf fibers, such as abaca and sisal; from shells from coconut, peanuts and walnuts; and corn stalks, wheat, oat, barley and oat chaff, and hemp. Suitably, the cellulosic fiber used is from a wood source. Suitable wood sources include softwood sources such as pines, spruces, cedar, and firs, and hardwood sources such as oaks, maples, eucalyptuses, poplars, beeches, and aspens. One or more cellulosic fibers may be used.
The cellulosic fibers may be screened through various screens, e.g., a 30-mesh or a 40-mesh screen, to obtain a mixture of different size fibers. The size of the fibers used in the composition of the invention ranges from about 10 to about 100 mesh, and preferably from about 40 to about 100 mesh.
The wood flours used in the composition include those obtained from soft and hard woods and combinations thereof. Preferable wood flours are from oak and pine, available as Oak 4037 (40 mesh) and Pine 402050 (40 mesh), respectively, from American Wood Fibers of Schofield, Wis. Another preferred wood flour is from maple.
Quaternary ammonium alkyl salt improves the internal and external lubricity of the plastic blends. The internal lubricity enhances the dispersion of the reinforcing filler in the polymer, thus improving the physical properties and increasing the extruder output. The principal benefit of the external lubricity is to improve the surface appearance of the extruded article by reducing the force needed to move the extrudable composition through the dye.
Quaternary ammonium alkyl salt also acts as an antimicrobial which improves decay resistance of the polymer-wood composites. They may be used with other biocides which include, but are not limited to, copper compounds, zinc compounds, azoles, isothiazolones, and carbamates.
Examples of known antimicrobial compounds which may be used with the quaternary ammonium alkyl salts are quaternary ammonium compounds such as diethyldodecylbenzyl ammonium chloride: dimethyloctadecyl-(dimethylbenzyl) ammonium chloride; dimethyldidecyl ammonium chloride; dimethyldidodecyl ammonium chloride; trimethyl-tetradecyl ammonium chloride; benzyldimethyl (C 12 -C 18 alkyl) ammonium chloride; dichlorobenzyldimethyldodecyl ammonium chloride; hexadecylpyridinium chloride; hexadecylpyridinium bromide; hexadecyltrimethyl ammonium bromide; dodecylpyridinium chloride, dodecylpyridinium bisulphate; benzyldodecyl-bis(betahydroxyethyl) ammonium chloride; dodecylbenzyltrimethyl ammonium chloride; benzyldimethyl (C 12 -C 18 alkyl) ammonium chloride; dodecyldimethylethyl ammonium ethylsulphate; dodecyldimethyl-(1-naphthylmethyl) ammonium chloride; hexadecyldimethylbenzyl ammonium chloride; dodecyldimethylbenzyl ammonium chloride and 1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantane chloride; urea derivatives such as 1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin; bis(hydroxymethyl) urea; tetrakis(hydroxymethyl) acetylene diurea; 1-(hydroxymethyl)-5,5-dimethylhydantoin and imidazolidinyl urea; amino compounds such as 1,3-bis(2-ethylhexyl)-5-methyl-5-aminohexahydropyrimidine; hexamethylene tetra amine; 1,3-bis(4-aminophenxoy)propane; and 2-[(hydroxymethyl)amino]ethanol; imidazole derivatives such as 1[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole; 2-(methoxycarbonylamino)benzimidazole; nitrile compounds such as 2-bromo-2-bromomethylglutaronitrile, 2-chloro-2-chloromethylglutaronitrile, 2,4,5,6-tetra-chloroisophthalodinitrile; thiocyanate derivatives such as methylene bis thiocyanate; tin compounds or complexes such as tributyltin-oxide, chloride, naphthoate, benzoate or 2-hydroxybenzoate; isothiazolin-3-ones such as 4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methylisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one, benzisothiazolin-3-one, 2-methylbenzisothiazolin-3-one, 2-octylisothiazolin-3-one, 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one; thiazole derivatives such as 2-(thiocyanomethylthio)-benzthiazole; and mercaptobenzthiazole; nitro compounds such as tris(hydroxymethyl)nitromethane; 5-bromo-5-nitro-1,3-dioxane and 2-bromo-2-nitropropane-1,3-diol; α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol (Cyproconazole); 1-[[2-(2,4-dichlorophenyl)4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (Propiconazole); α-[2-(4-chlorophenyl)ethyl]-α-phenyl-1H-1,2,4-triazole-1propanenitrile (Fenbuconazole); α-butyl-α-(4-chlorophenyl)-1H-1,2,4-triazole-1-propanenitrile (Myclobutanil); α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (Tebuconazole); 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone (Triadimefon); iodine compounds such as iodopropynyl butyl carbamate and tri-iodo allyl alcohol; aldehydes and derivatives such as glutaraldehyde (pentanedial), p-chlorophenyl-3-iodopropargyl formaldehyde and glyoxal; amides such as chloracetamide; N,N-bis(hydroxymethyl)chloracetamide; N-hydroxymethyl-chloracetamide and dithio-2,2-bis(benzmethyl amide); guanidine derivatives, such as, poly hexamethylene biguanide and 1,6-hexamethylene-bis[5-(4-chlorophenyl)biguanide]; thiones such as 3,5-dimethyltetrahydro-1,3,5-2H-thiodiazine-2-thione; triazine derivatives such as hexahydrotriazine and 1,3,5-tri-(hydroxyethyl)-1,3,5-hexahydrotriazine; oxazolidine and derivatives thereof, such as, bis-oxazolidine; furan and derivatives thereof such as 2,5-dihydro-2,5-dialkoxy-2,5-dialkylfuran; carboxylic acids and the salts and esters thereof such as sorbic acid and the salts thereof and 4-hydroxybenzoic acid and the salts and esters thereof; boric acids and its zinc complexes; phenol and derivatives thereof, such as, 5-chloro-2-(2,4-dichlorophenoxy)phenol; thio-bis(4-chlorophenol) and 2-phenylphenol; sulphone derivatives, such as, diiodomethyl-paratolyl sulphone, 2,3,5,6-tetrachloro-4-(methylsulphonyl) pyridine and hexachlorodimethyl sulphone; thioamides, such as, dimethyldithiocarbamate and its metal complexes, ethylenebisdithiocarbamate and its metal complexes, 2-mercaptopyridine-N-oxide and its metal complexes; and copper amine complexes including, but not limited to, ammonium/copper complexes, ethanolamine/copper complexes, diethanolamine/copper complexes, triethanolamine/copper complexes, diethylamine/copper complexes, ethylene diamine/copper complexes, and any combination of the foregoing.
From 0.001% to 3.0 wt. % based on weight of wood of other biocides may be added.
Coupling, compatabilizing, or mixing agents may advantageously be present in the polymeric composite. These additives may be present in an amount of from about 0.01 to about 20 wt. % based on the total weight of the composition, preferably, about 0.1 to about 10 wt. %, and most preferably from about 0.2 to 5 wt. % to achieve improvements in the physical, mechanical and thermal characteristics of the materials. A preferred compatabilizer is maleated polypropylene, present in an amount ranging from about 1 to about 5 wt. %. Talc may be present in an amount from about 2 wt. % to about 10 wt. %, based on the total weight of the composition. Other additives can be used, including viscosity stabilizers, inorganic fillers, processing aids, and coloring agents.
In addition to extrusion, the compositions of this invention may be injection molded to produce commercially usable products. The resultant product has an appearance similar to wood and may be sawed, sanded, shaped, turned, fastened and/or finished in the same manner as natural wood. It is resistant to rot and decay as well as termite attack and may be used, for example, as decorative moldings inside or outside of a house, picture frames, furniture, porch decks, window moldings, window components, door components, roofing systems and other types of structural members.
The following examples are illustrative of the invention:
EXAMPLE 1
Preparation of Quaternary Ammonium Lauryl Sulfate
A. Seventy grams of sodium lauryl sulfate (Aldrich® product 70% dodecyl sulfate, 25% tetradecyl sulfate and 5% hexadecyl sulfate) were added to 1000 ml of distilled water in a 2 liter flask equipped with a condenser. The mixture was stirred and slowly heated to about 60° C. After the sodium lauryl sulfate was completely dissolved in the water and the temperature of the solution reached 60° C., 100 grams of Barquat® MB-80 (80% active solution of alkyldimethylbenzyl ammonium chloride) were added to the solution. The resulting mixture was maintained at 60° C. for about 0.5 hour. A white precipitate of alkyldimethylbenzyl ammonium lauryl sulfate formed and was filtered. About 500 ml of distilled water was used to wash any residual sodium chloride on the precipitate. After washing, the precipitate was collected and left in a fume hood for 3 days for air-drying.
The structure of the alkyldimethylbenzyl ammonium lauryl sulfate was confirmed by nuclear magnetic resonance (NMR) analysis. The melting point was measured by differential scanning calorimeter. Since the composition contains an admixture of the material obtained from the dodecyl sulfate, tetradecyl sulfate, and hexadecyl sulfate, their melting points were detected for this compound, namely, 50° C., 100° C., and 130° C., respectively.
B. Didecyldimethyl ammonium lauryl sulfate was made by reacting didecyldimethyl ammonium chloride with sodium lauryl sulfate using the foregoing procedure.
The structure of didecyldimethyl ammonium lauryl sulfate was confirmed by NMR. The m.p. for this product is 45° C., 55° C., and 140° C.
C. The quaternary ammonium alkyl carboxylate, sulfonate, phosphate, and phosphite salts can be made by reacting a quaternary ammonium chloride with, as for example, sodium salts of alkyl carboxylate, alkyl sulfonate, alkyl phosphate, and alkyl phosphite, respectively, by following the above procedures.
The efficacy of aqueous solutions of alkyldimethylbenzyl ammonium lauryl sulfate and didecyldimethyl ammonium lauryl sulfate to inhibit fungus growth was evaluated by the agar plate method known in the art. Also tested were two commercially known biocides: didecyldimethyl ammonium chloride (Bardac® 2080) and alkyldimethylbenzyl ammonium chloride (Barquat® MB-80).
The results of the agar plate tests are shown in Table 2. The test data are reported as a percent inhibition (retardation) of the fungal growth.
TABLE 2 Conc. T . G . P . C . Sample ID ppm versicolor trabeum placenta globosum Didecyldimethyl 500 80.7 82.4 89.2 74.3 ammonium chloride Bardac ® 50 36.8 78.4 88.4 68.2 2080 Alkyl* dimethyl- 500 85.0 89.0 87.5 81.8 benzyl ammonium chloride 50 55.0 82.1 86.8 63.8 Barquat ® MB-80 Alkyl* dimethyl- 500 72.9 82.3 86.6 75.6 benzyl ammonium lauryl 50 32.2 51.7 83.0 64.5 sulfate Didecyldimethyl 500 81.3 80.8 86.0 78.7 ammonium lauryl sulfate 50 44.0 58.0 82.6 68.0 *40% C 12 , 50% C 14 and 10% C 16
The above table shows the lubricants of the present invention exhibit antifungal activity comparable to the two known commercial biocides tested.
EXAMPLE 2
Extruding Polymer-Wood Composites
In this example, an extrudable composition containing 40% HDPE (Petrothene reactor powder, Equistar®LB 0100-00) and 60% 40 mesh Pine 402050 (from American Wood Fibers of Schofield, Wis.) was mixed in a ten liter Henschel mixer for about three minutes at 1800 rpm. After mixing, the composites were dried for 16 hours at 100° C. in vacuum ovens under a vacuum of about 685 to about 710 mm Hg. Several samples were prepared by adding 3 phc (parts per hundred of composite) of the additives shown in Table 3 to the dried composite.
The dried compositions containing the additives were extruded through a rectangular profile 38.1×12.7 mm die in a 30 mm Werner & Pfleiderer co-rotating twin screw extruder. The extruder set temperature profile from the feed section to the die was 140°, 150°, 150°, 150°, 140° C. The composite material was fed to the extruder using a K-Tron S200 volumetric single screw feeder with a set feed rate of 16 kg/hr. The screw speed was set at 175 rpm. The extruded profile passed through a 0.65 m cooling chamber containing three sets of water sprays before being cut and collected.
The extruder torque is measured as a percent of the safe torque set for the extruder and the actual temperatures in zone 3 recorded as shown in Table 3 below. Zone 3 is the area of highest shear in the extruder. The amount of the temperature increase in this zone from the set temperature is a reflection of shear heating in the zone. A lower zone 3 temperature coupled with less extruder torque indicates an improved extruding process.
TABLE 3
Extruder
Temperature in
Additives
torque %
zone 3 (° C.)
3 phc Acrawax ® C/zinc stearate
64
164
(control)
3 phc Barquat LS*
56
156
1.5% Barquat LS plus 3 phc
55
159
Acrawax ® C/zinc stearate
3.0% Barquat LS plus 3 phc
49
152
Acrawax ® C/zinc stearate
3 phc Barquat LS plus 0.1% 8-
55
157
hydroxyquinoline, copper salt
1.5% DDA-LS plus 3 phc
56
159
Acrawax ® C/zinc stearate
3.0% DDA-LS plus 3 phc
46
153
Acrawax ® C/zinc stearate
*Barquat LS is for alkyl (40% C 12 , 50% C 14 , 10% C 16 dimethylbenzyl ammonium lauryl sulfate and is 100% active.
The data in the above table show that extruder torque percentages and the zone 3 temperatures for runs with alkyldimethylbenzyl ammonium lauryl sulfate, either alone or in combination with another additive, were lower than the extruder torque percent and the zone 3 temperature for the control.
The extruded samples were placed in water to determine how much water the samples absorb over time. Three extruded samples of each formulation, measuring 0.5×1½×2 inches were prepared and their central thickness and weight measured. Thereafter, the samples were totally immersed in 200 ml distilled water. After 7 days, the samples were removed from the water, weighed, and their central thickness again measured. The samples were returned to the water for an additional 33 days, after which time they were weighed and measured a third time. The percentages of the water uptake and thickness swelling were calculated as follows:
Water uptake %=(W 2 −W 1 )/W 1 ×100, where W 1 is the sample weight before soaking in the water and W 2 is the sample weight after soaking in the water.
Thickness swelling %=(T 2 −T 1 )/T 1 ×100 where T 1 is the central thickness of the sample before soaking in the water and T 2 is the central thickness of the sample after soaking in the water.
The average percent of the water uptake and thickness swell are shown in Table 4:
TABLE 4
Water uptake
Thickness Swell
Additives
7 days (%)
40 days (%)
7 days (%)
40 days (%)
3 phc Acrawax ® C/zinc stearate
7.65
17.69
1.65
6.03
(control)
3 phc Barquat LS
5.12
12.64
1.44
3.02
1.5% Barquat LS plus 3 phc
6.45
15.55
1.50
4.21
Acrawax ® C/zinc stearate
3.0 Barquat LS plus 3 phc
5.71
14.14
1.45
3.92
Acrawax ® C/zinc stearate
3 phc Barquat LS plus 0.1% 8-
5.25
11.80
1.45
3.93
hydroxyquinoline, copper salt
1.5% DDA-LS plus 3 phc
7.02
17.52
1.58
5.36
Acrawax ® C/zinc stearate
3.0% DDA-LS plus 3 phc
7.52
16.42
1.56
5.23
Acrawax ® C/zinc stearate
As shown in Table 4, the composites made with Barquat LS either alone or in combination with another additive absorbed less water and had less thickness swell than the control alone.
The efficacy of extruded samples containing alkyldimethylbenzyl ammonium lauryl sulfate or didecyldimethyl ammonium lauryl sulfate to inhibit fungal growth was evaluated by the standard soil block test method (American Wood Preservation Association E10) known in the art. The biocide effectiveness is determined by % weight loss in wood component of the tested samples. The sample blocks (13 mm×14 mm×14 mm) were exposed to the brown-rot fungus G. trabeum for 22 weeks, with four replicates per treatment.
The results, presented in Table 5, clearly show that the extruded samples containing alkyldimethylbenzyl ammonium lauryl sulfate or didecyldimethyl ammonium lauryl sulfate had significantly lower weight loss than the control samples which contain the conventional lubricant (N,N ethylene bis-stearamide and zinc stearate). This illustrated that the addition of alkyldimethylbenzyl ammonium lauryl sulfate or didecyldimethyl ammonium lauryl sulfate inhibits brown-rot fungal growth to a substantially great extent.
TABLE 5
Summary of Average Percentage of Weight Loss
for Extruded Woodfiber Plastic Composites
(60% of Pine Powder and 40% of HDPE)
Average weight loss
Additives
(%)
3 phc Acrawax ® C/zinc stearate
21.0
3 phc Acrawax ® C/zinc stearate
1.7
with 1.5% Barquat-LS (based on
wood weight)
3 phc Acrawax ® C/zinc stearate
1.7
with 3.0% Barquat-LS (based on
wood weight)
3 phc Barquat-LS
1.4
3 phc Barquat-LS with 0.1% 8-
0.9
hydroxyquinoline, copper salt
(based on wood weight)
3 phc Acrawax ® C/zinc stearate
2.8
with 1.5% DDA-LS (based on
wood weight)
3 phc Acrawax ® C/zinc stearate
2.5
with 3.0% DDA-LS (based on
wood weight)
Samples containing the blend of alkyldimethylbenzyl ammonium lauryl sulfate and 8-hydroxyquinoline, copper salt (40:1 by weight) further decreased fungal growth, indicating that 8-hydroxyquinoline, copper salt, which is a wood preservative, functions as a biocide enhancer when combined with alkyldimethylbenzyl ammonium lauryl sulfate. This experiment supports that the use of other biocides as an antimicrobial enhancer with alkyldimethylbenzyl ammonium lauryl sulfate increase the biocidal activity of the combination.
All patents, applications, articles, publications, and test methods mentioned above are hereby incorporated by reference.
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The invention relates to a polymer-cellulosic fiber composition comprising a polymer, a cellulosic fiber, and a quaternary ammonium alkyl salt wherein the latter imparts antimicrobial properties to the composition and functions as a lubricant during the formation of the composition. The quaternary ammonium alkyl salts may be alkyl carboxylate, alkyl sulfate, alkyl sulphonate, alkyl phosphate, or alkyl phosphite. Certain of the salts are new compositions of matter. The method of extruding and the extrudate are also claimed.
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FIELD OF THE INVENTION
This invention relates to computer systems, and more particularly to touch activated display screens.
BACKGROUND OF THE INVENTION
In certain situations, it is advantageous to control the operation of computer systems using "touchscreen" technologies. For example, touch activated information systems in public places do not require a keyboard or mouse, or other similar hard-to-use and easy-to-damage control devices.
In touch activated computer applications, the system displays images on a screen of a display terminal. The images can include visual option icons or "buttons," with appropriate legends. The user can activate processes corresponding to the visual buttons by pointing at, or "touching" the screen where the buttons are displayed.
Previous touch activated systems have generally sensed the presence of a finger, or pointing device on or near the display screen using capacitance, resistive, acoustic, mechanical, or optical sensors mounted directly on the screen, or around the periphery of the screen, for example, in the bezel of the display terminal.
These sensing techniques generally require a physical modification of the display terminal. For example, in capacitive and resistive systems, transparent layers of conductive and dielectric films are placed directly on the screen. With systems that are acoustically or optically activated, the transmitters and receivers are generally mounted in the bezel or housing surrounding the screen.
The problem with the prior art touch technologies is that the display terminal must be physically modified at an increased cost to receive the sensors. Specialized sensor interfaces and software must also be generated. It is desired to provide a touch activated system without the need to modify the display terminal.
SUMMARY OF THE INVENTION
The invention enables the activation of computer applications by pointing at or touching specific portions of a screen of a display terminal. A computer program displays an image on the screen. The image includes one or more visual option buttons, each button corresponding to a specific application program to be activated.
During operation of the system, a camera captures digitally encoded frames of a scene in from of the screen. The frames can include calibration frames, and selection frames. Each frame includes a plurality of digitally encoded pixels arranged in a regularized pattern. The pixels encode light intensity values.
While someone is "pointing" at the screen, the pixel values of a reference frame are compared with the pixels of a subsequent selection frame. The frames can be compared using image registration techniques. A specific computer application is selected for execution if the difference between the pixel values of a predetermined portion of the reference frame, and a corresponding portion of the selection frame exceeds a predetermined threshold value.
In one aspect of the invention, the camera is mounted above the display terminal with the lens pointing in a downward direction. The optical axis of the lens is in front of the screen. This allows for the detection of pixel motion in vertically oriented stripes or zones. If the camera is mounted along side the terminal pointing sideways, then the detection stripes or zones can be arranged horizontally.
In another aspect of the invention, a mirror is mounted in the scene viewed by the camera. The mirror is mounted at such an angle that the frames captured by the camera include a different view of the seen as reflected in the mirror. For example, if the mirror is mounted at an angle of about 45° with respect to the optical axis, then the view in the mirror is substantially perpendicular to the directly viewed scene. Pixels corresponding to the different view can be separately compared to allow application selection using a two-dimensional arrangement of the visual display buttons.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block schematic of an image-based touch activated computer system according to the invention;
FIG. 2 is an image shown on a screen of the system of FIG. 1;
FIGS. 3-5 represent frames grabbed by a camera of the system of FIG. 1;
FIG. 6 is a schematic diagram of a touch activated system using a mirror; and
FIG. 7 is a frame grabbed by the system of FIG. 6.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
As shown in FIG. 1, an image-based touch system 100 includes a display terminal 110 having a display screen 112, an image processing system 120, and a storage subsystem 130. A camera 140 is centrally mounted above the display terminal 110 such that the lens 141 is substantially pointing downward. The optical axis 142 of the lens 141 is substantially parallel to the plane of display screen 112, and slightly in front of the screen 112.
The image processing subsystem 120 includes a video board 122 connected to the camera 140. The video board 122 includes an analog-to-digital (A/D) convertor, and a frame buffer (FB) for storing frames. The image processing subsystem 120 also includes an image processor 126 and an image buffer (IB) 125. The image processing subsystem 126 can include one or more central processing units (CPUs) connected to local dynamic random access memories (DRAM) by busses. The storage subsystem 130 can be used to persistently store programs and data used by the image processing subsystem 120 in a database (DB).
The operation of the system 100 is now described also with reference to FIGS. 2 and 3. The image processing subsystem 120 creates an image 200 in the image buffer 125 for display on the screen 112 of the terminal 110. The image 200 includes a plurality of visual option "buttons" 201-205 with appropriate legends, and an optional an instruction field 210.
As the image 200 is displayed, the camera 140 periodically captures or "grabs" frames, e.g., frame 300 of FIG. 3, representing the scene, generally indicated by reference numeral 10, in front of the display screen 112. The scene 10 is converted to digital signals which are stored as frames in the buffer 121 as a regularized pattern of pixels 301, for example, an array of 640×480 pixels. Each pixel 301 has an intensity value corresponding to a level of optical illumination of the scene.
FIG. 3 shows a "reference" frame 300 which is captured by the camera 110. The reference frame 300 includes three general portions 310, 320, and 330. The portions 310 (hashed) corresponds to the view of the top of the display terminal 110. Portion 320 corresponds to a narrow strip of the scene 10 immediately in front of the screen 112, e.g., the portion of the scene 10 which is closest to the optical axis 112 of the camera 140. The interface between portions 310 and 320 generally corresponds to a plane just in front of the surface of the screen 112. As will be described in further detail below, the width of the portion 320 can be adjusted to match an appropriate level of sensitivity to an actual "touching" of the screen 112. The portion 330 is that part of the scene 10 the furthest away from the screen 112. The pixels 301 of the reference frame 300 can be stored by the processing system 120 for later use.
The portion 320 of the frame 300 can be subdivided into a plurality of touch zones (TZ) 321-325 which are substantially aligned in front of the displayed visual option buttons 201-205 to provide "activation" areas. Each of the zones 321-325, for a particular visual button size, can be about 64×64 pixels.
In response to viewing the image 200 on the display screen 112, a user of the system 100, "points" at one of the visual buttons 201-205 using a finger or a pointing device. As the user is pointing at the screen 112, the scene 10 is captured as a sequence of frames by the camera 114. As described below, the rate of frame grabbing can depend on how fast the scene 10 is changing.
The selection frames are compared with the reference frame 300 to determine differences in pixel intensity values in the touch zones. Pixel differences can be determined using well known image registration techniques as described in U.S. Pat. No. 4,644,582, Image Registration Methods issued to Morishita et al., on Feb. 17, 1987, U.S. Pat. No. 5,048,103, Method for Automatic Resetting of Images, issued to LeClerc et al., on Sep. 10, 1991, U.S. Pat. No. 5,067,015, Method of Processing Video Image Data for use in the Storage or Transmission of Moving Digital Images, or as described in Registration of Images with Geometric Distortions, by A. Goshtabashy, IEEE Transactions on Geoscience and Remote Sensing, Vol. 26, No. 1, January 1988. Pixel differences can be used to detect localized "motion" or optical flow in the scene 10.
The rate at which frames can be grabbed can be determined by the relative total pixel difference between any two successive frames. If the pixel difference becomes larger than some predetermined threshold, a new reference frame can be grabbed for comparison with subsequent selection frames. The process of grabbing a new reference frame can be considered a recalibration step.
For example, selection frame 400 of FIG. 4 shows a hand and finger 410 entering the portion 330 of the scene 10 well away from the screen 112. Any substantial pixel motion in this portion exceeding a predetermined threshold can trigger a closer examination of the selection frames.
Selection frame 500 of FIG. 5 shows the finger 410 entering the touch zone 332. Pixel motion in this particular zone corresponds to the user pointing at the visual button 202 on the screen. Actual activation of a predetermined application processes of the system 100 can be triggered by the pixel motion in, for example, zone 322 "reaching" the interface 501 between zone 322 and portion 310. Sensitivity to actual touching of the screen 112 can be adjusted by varying the width of the portion 320. For example, if the touch zones 321-325 have a pixel size of 64×8 application actuation can be made to approximately coincide with the actual instantaneous touching of the screen 112.
As an advantage, the image-based touchscreen as described above can be adapted to almost any display terminal without a physical modification of the terminal itself. The camera 140 can be mounted on a bracket attached to the terminal, or on a tripod or other similar camera mounting support mechanism separate from the terminal.
This type of arrangement is well suited for a public kiosk which may already include an imaging subsystem for sensing the presence of a person in the kiosk or information booth.
It should be understood, that the camera 140 can be mounted on the side of the terminal 110 with the optical axis 142 having a horizontal orientation. In this case, the visual option buttons can be arranged in a vertical pattern.
In an alternative embodiment, as shown in schematically in FIG. 6, a mirror 610 is also mounted on the side of the display terminal 140 so that the mirror is in the scene 10 viewed by the camera. The mirror 140 is angled, for example at 45° with respect to the optical axis, such that a first angular portion 620 of the scene, e.g., the portion 620 between solid ray lines 621-622 lines, captures a horizontal view of the scene 10, and a second angular portion 630 between dashed ray lines 631-632 captures the vertical view of the scene as shown in FIG. 1. In this case, the image displayed on the terminal 120 can be a two-dimensional array of visual option n button s 601-609.
FIG. 7 shows the corresponding reference frame 700. In the frame 700, a portion 720 of the scene is viewed horizontally across by the camera 140 via the mirror 610, and the portion 730 is directly viewed vertically down from the camera. The portion 720 can include touch zones 721-723, and the portion 730 includes touch zones 731-733. A modified image registration technique can be used to simultaneously detect pixel motion in zones 721-723 and zones 731-733. Pixel motion in zones 721 and 731 corresponds to button 601 being touched, while pixel motion in zones 723 and 733 corresponds to touching button 609, and so forth.
It should be understood that the mirror 610 can be mounted at other angles which are sufficient to detect localized motion for pixel portions in a two-dimensional arrangement using triangulation techniques. Two-dimensional motion detection can also be done using two cameras mounted at different angles with respect to each other. In this case, each camera can capture a different view of the scene, and the frames of the two cameras can be calibrated and compared with each other to determine two-dimensional pointing or touching activities.
It is understood that the above-described embodiments are simply illustrative of the principles of the invention. Various other modifications and changes may be made by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
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In a touch activated computer system, a display terminal displays an image on a screen of the terminal. The image includes one or more visual option buttons arranged in a predetermined pattern. Each button corresponds to a specific application program which can be executed by the system. A camera has a lens oriented to capture frames representing a scene in front of the screen. Each frame includes a plurality of regularized pixel values. The system includes an image registration subsystem for comparing the pixel values of successive frames. A particular application is selected for execution when the pixel values corresponding to that portion of the scene directly in front of a particular button differ in successive frames more than a predetermined threshold value.
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[0001] The present application is a continuation-in-part of U.S. patent application Ser. No. 09/483,550, filed Jan. 14, 2000.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention relates to the field of biologically active peptide containing compositions for use in the prevention and treatment of hematopoietic neoplastic diseases, particularly leukemia.
[0004] 2. Description of Related Art
[0005] LFA-1 (lymphocyte function associated antigen-1) is an integrin αβ heterodimer (Carlos and Harlan, 1994; Springer, 1994; Larson and Springer, 1990; McEver, 1990; Picker and Butcher, 1992). Although three other integrins restricted in expression to leukocytes share the same β subunit and have homologous α subunits (Mac-1, p150,95, and alpha d), only LFA-1 is expressed on normal and leukemia T cells (Larson and Springer, 1990). LFA-1 binds ICAM-1 (intracellular adhesion molecule), and although LFA-1 is constitutively expressed on all leukocytes, LFA-1 binding to ICAM-1 requires cellular activation. Activation, in part, results in conformational changes in LFA-1 that affect its avidity for ICAM-1. In contrast, ICAM-1 is constitutively avid and expressed on a wide array of cell types including leukocytes, endothelium, stromal cells, and fibroblasts. In a model developed by the present inventor, a stromal cell derived soluble factor cooperates with LFA-1 on the surface of T lineage acute lymphoblastic leukemia (T-ALL) cells (Winter et al., 1998). The LFA-1 on T-ALL cells results in bone marrow (BM) stromal cell binding via ICAM-1 that leads to enhanced leukemia cell survival. Furthermore, aberrant LFA-1/ICAM-1 dependent interaction between circulating leukemia cells and endothelial cells lining blood vessels promotes extravasation of leukemia cells into tissue as seen in the life-threatening therapeutic complication of acute leukemia, retinoic acid syndrome (Brown et al., 1999). Hence, the development of effective in vivo inhibitors of LFA-1/ICAM interaction would be useful in the therapy of acute leukemia and prevention of therapeutic complications.
[0006] The present inventor has shown, for example, that inhibition of LFA-1/ICAM-1 dependent stromal cell binding with mAbs decreases survival of T-ALL cell lines and T-ALL cells isolated from patients. In one study, a representative sample from a patient with T-ALL showed that survival of T-ALL cells is augmented by BM stromal cells and that survival is inhibited by mAbs directed against LFA-1 (mAb TSI/22,5 μg/ml) or its ligand ICAM-1 (mAb 84H10, 10 μg/ml). This observation has been replicated for T-ALL cell lines Jurkat and Sup T I as well as a subset of patients with T-ALL. However, even though in vivo use of mAbs against LFA-1 or ICAM-1 blocks LFA-1 function in a number of disease models, unfortunately anaphylactic reactions and secondary physiologic effects have hampered this approach (McMuray, 1996; DeMeester: et al., 1996; Jackson et al., 1997; Cuthbertson et al., 1997; Gundel et al., 1992; Haming et al., 1993; Nakano et al, 1995).
[0007] Another means to interfere with protein-protein interactions is through the use of small peptide inhibitors. In fact, small peptide inhibitors to adhesion molecules structurally-related to LFA-1 have recently been approved for clinical use in coagulopathies (Ohman et al., 1995; Adgey et al., 1998; Leficovis and Topol, 1995). Short linear peptides (<30 amino acids) have also been described that prevent or interfere with integrin dependent firm adhesion using sequences derived from integrin or their ligands. In particular, these peptides have been derived from a number of integrin receptors: the β2 and β3 subunits of integrins, and the aiib subunit of ICAM-1, and VCAM-1 (Murayama et al., 1996; Jacobsson and Frykberg, 1996; Zhang and Plow, 1996; Budnik et al., 1996; Vanderslice et al, 1997; Suehiro et al., 1996; Endemann et al., 1996). However, the clinical applicability of these linear peptides is limited. The half maximal inhibitory concentration (IC 50 ; concentration at which aggregation is inhibited 50%) for most of these peptides is 10 −4 M with purified receptor-ligand pairs (univalent interactions) and they are ineffective at inhibiting multivalent interactions, during cell-cell adhesion. In addition, linear peptides have short serum half-lives because of proteolysis. Therefore, prohibitively high concentrations of peptide would have to be administered in a clinical setting and a biologic effect would not necessarily occur.
[0008] Longer peptides, ranging in length from 25-200 residues, have also been reported to block β1, β2, and β3 integrin dependent adhesion (Zhang and Plow, 1996; Budnik et al., 1996; Vanderslice et al, 1997; Suehiro et al., 1996; Endeman et al., 1996). In general, these peptide inhibitors may have higher affinities or slower off-rates than short peptides and, therefore, are better inhibitors. However, they are still susceptible to proteolysis.
[0009] Therefore, a need exists to develop novel and specific classes of pharmaceutical agents to inhibit the binding of LFA-1 and ICAM-1 and to be useful in the treatment of hematopoietic neoplastic diseases as well as other diseases that involve emigration of leukocytes from blood into tissue, such as myocardial infarction, radiation injury, asthma, rheumatoid arthritis, and lymphoma metastasis.
SUMMARY
[0010] The present invention addresses the problems in the art by providing compositions that include cyclic peptide inhibitors of binding interactions between the integrin, lymphocyte function associated antigen-1 (LFA-1) expressed on leukocytes, including leukemic T-cells, and intracellular adhesion molecule 1 (ICAM-1), expressed on a variety of cell types. As stated above, this binding of activated LFA-1 is implicated in a variety of diseases and inhibition of this binding interaction with a cyclic peptide inhibitor will have implications in the treatment or management of those diseases.
[0011] As a part of the present invention, phage display has been used to identify peptide sequences that bind ICAM-1 and block LFA-1/ICAM interaction. Phage that specifically bound ICAM-1 were identified by repeated selection from a cysteine-constrained heptapeptide phage display library. The peptide sequences expressed on ICAM-1 binding phage were determined by nucleotide sequencing. A consensus sequence, CLLRMRSIC (SEQ ID NO:1) was derived from the analysis of the most frequently occurring sequences. Analysis of less frequently recurring amino acids of ICAM-1 binding-phage identified variants of SEQ ID NO: 1 wherein the second amino acid is methionine (SEQ ID NO: 17), or in which the 5 th amino acid is proline (SEQ ID NO: 5), or in which the 6 th amino acid is asparagine (SEQ ID NO: 9), or in which the 7 th amino acid is leucine (SEQ ID NO: 3), or in which the 8 th amino acid is arginine (SEQ ID NO: 2), or any combination of these substitutions.
[0012] Another aspect of the present disclosure is the application of an alanine screening technique to the consensus sequence, SEQ ID NO: 1. An alanine was substituted at each position in the hepatapeptide LLRMRSI of the consensus sequence SEQ ID NO: 1, and each peptide was examined in for its ability to inhibit LFA-1/ICAM-1 mediated cell aggregation. Alanine substitution of the isoleucine at position 8 of SEQ ID NO: 1, i.e., CLLRMRSAC (SEQ ID NO: 40), resulted in a more potent antagonist. Loss of inhibitory function resulted from alanine substitution of the leucines in positions 2 (SEQ ID NO: 34) and 3 (SEQ ID NO: 35), methionine in position 5 (SEQ ID NO: 37), and arginine in position 6 (SEQ ID NO: 38) of SEQ ID NO: 1, indicating that these amino acids are important to the antagonistic activity of the peptide. Substitution of the serine in position 7 (SEQ ID NO: 39) had no significant effect on the inhibitory activity of the peptide. Substitution of the arginine in position 4 (i.e., SEQ ID NO: 36) of SEQ ID NO: 1 was not soluble in aqueous solution at 1 nm and was not tested.
[0013] A further aspect of the present invention is the use of conservative amino acid substitutions of the key amino acid residues identified by the alanine screen. Sequences that exhibit greater inhibition of LFA-1/ICAM-1 mediated cell inhibition as compared to SEQ ID NO: 1, include CILRMRSAC (SED ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO 45), CLLRMKSAC (SEQ ID NO: 46), and CLLRMRSVC (SEQ ID NO: 48).
[0014] The present invention may be described, therefore, in certain aspects as a composition comprising a cyclic peptide inhibitor of LFA-1/ICAM-1 interaction, wherein the composition has the amino acid sequence, CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof. Conservative variants are described elsewhere herein, and include the exchange of an amino acid for another of like charge, size, or hydrophobicity, and include, but are not limited to, CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SED ID NO: 44), CLLKMRSAC (SEQ ID NO 45), CLLRMKSAC (SEQ ID NO: 46), and CLLRMRSVC (SEQ ID NO: 48). The present disclosure would also include variants of SEQ ID NO: 1 in which the 3 rd and 4 th amino acids remain the same and other amino acids of the sequence are substituted and tested empirically for their ability to inhibit the LFA-1/ICAM-1 interaction. The amino acid sequence is numbered in the conventional sense, in that the first amino acid on the N-terminus is cysteine, followed by 7 amino acids and then a carboxy terminal cysteine. In the practice of the invention, the two terminal cysteines may form a disulfide bonded cystine residue resulting in a cyclic peptide as is well known in the art. Alternatively, the terminal cysteines may be linked by an amide peptide linkage, either directly or separated by one or more amino acids, leaving two free sulfhydryl groups.
[0015] Based on the empirical data obtained by the inventor and disclosed herein, a cyclic peptide of the invention may have the sequence of SEQ ID NO: 1, or it may be a derivative of that sequence in which the second amino acid is methionine (SEQ ID NO: 17), or in which the 5 th amino acid is proline (SEQ ID NO: 5), or in which the 6 th amino acid is asparagine (SEQ ID NO: 9), or in which the 7 th amino acid is leucine (SEQ ID NO: 3), or in which the 8 th amino acid is arginine (SEQ ID NO: 2), or any combination of these substitutions, or even conservative variants of any of these substitutions.
[0016] Another aspect of the present invention includes cyclic peptides inhibitors of LFA-1/ICAM-1 interaction comprising the heptapeptide sequences which include LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO: 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID NO: 54) or LLRMRSV (SEQ ID NO: 55). Peptides that comprise the heptapeptide sequences of the present invention may be a peptide of 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14, or 15 amino acids in length, wherein additional amino acids may be any L-series or any D-series amino acid.
[0017] In preferred embodiments of the invention, the peptides or peptide mimetics of the invention exhibit an inhibition constant (IC 50 ) for the binding interaction of LFA-1/ICAM-1 of from about 10 μM to about 800 μM for cell aggregation or from about 10 to about 250 nM for monovalent ICAM-1 binding. The term “IC 50 ” is well known in the art, and means the half maximal inhibitory concentration, or concentration at which aggregation is inhibited by 50%.
[0018] Any of the compositions described herein may be formulated for pharmacological or therapeutic administration either to a mammal, or more preferably to a human. As such, the compositions may be contained in a pharmaceutically acceptable carrier. The preferred mode of administration of a peptide active agent is by injection, either intravenous, intra-arterial, intramuscular or subcutaneous. Other routes of administration may also be possible and would be included within the scope of the present disclosure.
[0019] The compositions may be administered parenterally or intraperitoneally. Solutions of the active compounds as free base or pharmacologically acceptable salts can be prepared in water suitably mixed with a surfactant, such as hydroxypropylcellulose. Dispersions can also be prepared in glycerol, liquid polyethylene glycols, and mixtures thereof and in oils. Under ordinary conditions of storage and use, these preparations contain a preservative to prevent the growth of microorganisms.
[0020] The pharmaceutical forms suitable for injectable use include sterile aqueous solutions or dispersions and sterile powders for the extemporaneous preparation of sterile injectable solutions or dispersions. In all cases the form must be sterile and must be suitably fluid. It must be stable under the conditions of manufacture and storage and must be preserved against the contaminating action of microorganisms, such as bacteria and fungi. The carrier can be a solvent or dispersion medium containing, for example, water, ethanol, polyol (for example, glycerol, propylene glycol, and liquid polyethylene glycol, and the like), suitable mixtures thereof, and vegetable oils. The proper fluidity can be maintained, for example, by the use of a coating, such as lecithin, by the maintenance of the required particle size in the case of dispersion and by the use of surfactants. The prevention of the action of microorganisms can be brought about by various antibacterial and antifungal agents, for example, parabens, chlorobutanol, phenol, sorbic acid, thimerosal, and the like. In many cases, it will be preferable to include isotonic agents, for example, sugars or sodium chloride. Prolonged absorption of the injectable compositions can be brought about by the use in the compositions of agents delaying absorption, for example, aluminum monostearate and gelatin.
[0021] Sterile injectable solutions are prepared by incorporating the active compounds in the required amount in the appropriate solvent with various of the other ingredients enumerated above, as required, followed by filtered sterilization. Generally, dispersions are prepared by incorporating the various sterilized active ingredients into a sterile vehicle which contains the basic dispersion medium and the required other ingredients from those enumerated above. In the case of sterile powders for the preparation of sterile injectable solutions, the preferred methods of preparation are vacuum-drying and freeze-drying techniques which yield a powder of the active ingredient plus any additional desired ingredient from a previously sterile-filtered solution thereof.
[0022] As used herein, “pharmaceutically acceptable carrier” includes any and all solvents, dispersion media, coatings, antibacterial and antifungal agents, isotonic and absorption delaying agents and the like. The use of such media and agents for pharmaceutical active substances is well known in the art. Except insofar as any conventional media or agent is incompatible with the active ingredient, its use in the therapeutic compositions is contemplated. Supplementary active ingredients can also be incorporated into the compositions.
[0023] A peptide can be formulated into a composition in a neutral or salt form. Pharmaceutically acceptable salts, include the acid addition salts (formed with the free amino groups) and which are formed with inorganic acids such as, for example, hydrochloric or phosphoric acids, or such organic acids as acetic, oxalic, tartaric, mandelic, and the like. Salts formed with the free carboxyl groups can also be derived from inorganic bases such as, for example, sodium, potassium, ammonium, calcium, or ferric hydroxides, and such organic bases as isopropylamine, trimethylamine, histidine, procaine and the like.
[0024] For parenteral administration in an aqueous solution, for example, the solution should be suitably buffered if necessary and the liquid diluent first rendered isotonic with sufficient saline or glucose. These particular aqueous solutions are especially suitable for intravenous, intramuscular, subcutaneous and intraperitoneal administration. In this connection, sterile aqueous media which can be employed will be known to those of skill in the art in light of the present disclosure. For example, one dosage could be dissolved in 1 mL of isotonic NaCl solution and either added to 1000 mL of hypodermoclysis fluid or injected at the proposed site of infusion, (see for example, “Remington's Pharmaceutical Sciences” 15th Edition, pages 1035-1038 and 1570-1580). Some variation in dosage will necessarily occur depending on the condition of the subject being treated. The person responsible for administration will, in any event, determine the appropriate dose for the individual subject.
[0025] It is an aspect of the present disclosure that the disclosed compositions may be used in adjunct therapy in standard treatments for diseases such as hematopoietic neoplasms. The present invention may be described therefore, in certain embodiments as a method of preventing retinoic acid syndrome in a subject receiving all-trans retinoic acid, comprising administering to the subject an effective amount of a composition comprising a cyclic peptide, wherein the peptide comprises a heptapeptide sequence including, but not limited to, LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO: 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID NO: 54) or LLRMRSV (SEQ ID NO: 55). In some embodiments the cyclic peptide has the amino acid sequence CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof, such as CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), or CLLRMRSVC (SEQ ID NO: 48).
[0026] An embodiment of the invention may also be described as a method for inhibiting growth of leukemia cells comprising preventing an LFA-1/ICAM-1 interaction between the leukemia cells and support cells such as bone marrow stromal cells, wherein the method comprises contacting the leukemia cells with a cyclic peptide inhibitor of the LFA-1/ICAM-1 interaction, and further wherein the amino acid sequence of the cyclic peptide inhibitor is not a fragment of the amino acid sequence of LFA-1 or ICAM-1. In the practice of this method, the leukemia cells are preferably in a leukemia patient and contacting comprises administering the cyclic peptide to the patient.
[0027] An embodiment of the invention is also a therapeutic package for dispensing to, or for use in dispensing to, a mammal or human being treated for a hematopoietic neoplastic disease, myocardial infarction, radiation injury, asthma, rheumatoid arthritis, or lymphoma metastasis, wherein the package contains in a unit dose, an amount of a cyclic peptide comprising a heptapeptide sequence including, but not limited to, LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO: 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID NO: 54) or LLRMRSV (SEQ ID NO: 55), effective to inhibit an LFA-1/ICAM-1 interaction in a subject when administered periodically. In some embodiments the cyclic peptide has the amino acid sequence CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof, such as CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), or CLLRMRSVC (SEQ ID NO: 48). In certain embodiments a unit dose is from about 10 to about 500 μg/Kg, or is from about 50 to about 250 μg/Kg, or from about 120 to about 150 μg/Kg. The unit dose may be an initial bolus dose which may be followed by a continuous infusion of about 5 to about 250 μg/Kg/min, or from about 40 to about 60 μg/Kg/min, or may be about 50 μg/Kg/min. Alternatively, unit doses may be repeated daily, and administered multiple times per day. Dosage regimens are not limited to those exemplified, and the invention encompasses any dosage regimen that delivers an therapeutically effective dose. An example of clinical administration of a peptidomimetic inhibiting an integrin functions is documented by Ohman et al. (1995).
[0028] An embodiment of the present disclosure is a method of inhibiting emigration of leukocytes from blood into tissue in a subject comprising administering to the subject an amount of a cyclic peptide comprising a heptapeptide sequence including, but not limited to, LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID: 54) or LLRMRSV (SEQ ID NO: 55), effective to inhibit an LFA-1/ICAM-1 interaction in the subject. In some embodiments the cyclic peptide has the amino acid sequence, CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof, such as CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO 45), CLLRMKSAC (SEQ ID NO:46), or CLLRMRSVC (SEQ ID NO: 48). In preferred embodiments the subject is susceptible to the development of or is suffering from a hematopoietic neoplastic disease, myocardial infarction, radiation injury, asthma, rheumatoid arthritis, or lymphoma metastasis.
[0029] A further embodiment of the invention is a method comprising a competitive binding assay for screening the ability of candidate compounds to bind to ICAM-1. The method comprises assessing the displacement of candidate compounds by cyclic petide inhibitors of LFA-1/ICAM-1 binding interaction. The cyclic peptide may comprise a heptapeptide sequence including, but not limited to, LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID NO: 54) or LLRMRSV (SEQ ID NO: 55). In some embodiments the cyclic peptide has the amino acid sequence, CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof, such as CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), or CLLRMRSVC (SEQ ID NO: 48).
[0030] Other embodiments of the present disclosure include methods of therapy relating to tissue allografts such as renal, heart and thryoid allografts, bone marrow transplants, diabetes, rheumatoid arthritis, psoriasis, T-cell mediated sensitization reactions such as contact sensitization, and other T-cell mediated disorders. Such methods comprise comprising administering to the subject an amount of a cyclic peptide comprising a heptapeptide sequence including, but not limited to, LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRNIRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO: 52), LLRMKSA (SEQ ID NO:53), ILRMRSA (SEQ ID NO: 54) or LLRMRSV (SEQ ID NO: 55), effective to inhibit an LFA-1/ICAM-1 interaction in the subject. In some embodiments the cyclic peptide has the amino acid sequence, CLLRMRSIC (SEQ ID NO: 1) or CLLRMRSAC (SEQ ID NO: 40), or a conservative variant thereof, such as CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), or CLLRMRSVC (SEQ ID NO: 48).
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
[0032] [0032]FIG. 1 is a bar graph display of data showing aggregation of JY cells being inhibited by either mAbs against LFA-1, or by titration of 100 μM to 1 mM of the consensus peptide CLLRMRSIC (SEQ ID NO: 1). A randomized peptide, CLMIRMLRC (SEQ ID NO: 33) at a concentration of 1 mM is shown to be ineffective.
[0033] [0033]FIG. 2 is a schematic of the phage display methodology wherein a phage library with random peptide sequences is screened for ability to bind to purified ICAM-1.
[0034] [0034]FIG. 3 represents the structure of a carboxy fluorescein derivative of the disulfide constrained cyclic form of SEQ ID NO: 46.
DETAILED DESCRIPTION
[0035] Hematopoietic neoplasms including acute leukemia constitute 7% of male and 6% of female cancer (Ries et al., 1994). If untreated, the clinical course of acute leukemia is rapidly fatal. Drugs to treat acute leukemia usually interfere with cell replication, and as a result, these drugs have nor-specific physiologic consequences and undesirable side effects. One of the fundamental problems in the development of novel leukemia therapies is the identification of pharmaceutical targets and the production of pharmaceutical agents against those targets. The present inventor has shown that LFA-1 and ICAM-1 are molecular targets for use in the therapy of acute leukemia using two assays that recapitulate the molecular and cellular events leading to leukemia cell proliferation in the marrow and spread of leukemia cells to distant sites. The first assay simulates the marrow microenvironment. In this assay, T lineage acute lymphoblastic leukemia (T-ALL) cells isolated from patients are co-cultured with bone marrow (BM) stromal cells that support hematopoiesis. T-ALL cells isolated from patients will die in ex vivo culture, and BM stromal cells have been shown to support ex vivo survival of T-ALL cells. Furthermore, in co-culture experiments mAbs to LFA-1 and ICAM-1 dramatically decrease T-ALL cell survival by inhibiting adherence to bone marrow stromal cells. This latter finding indicates that survival of T-ALL cells in the marrow microenvironment is dependent on proper LFA-1/ICAM-1 binding. Since failure to eradicate leukemia cells in the marrow is a major reason for treatment failure, adjunct therapy that included inhibition of LFA-1/ICAM-1 ligation between leukemia cells and T-ALL cells may cause T-ALL cell death and improved patient outcome. This may have applicability to all T-cell leukemias.
[0036] The present inventor has also established a model and dissected the mechanism of a life-threatening therapeutic complication of acute promyelocytic leukemia (APL), retinoic acid syndrome. All-trans retinoic acid (ATRA) promotes a complete remission in up to 80% of patients with APL. However, retinoic acid syndrome occurs in up to 30% of patients and is caused by APL cells infiltrating organs after retinoic acid therapy. Using an apparatus known as a parallel plate flow chamber, the interactions that occur in blood vessels between circulating leukemia cells and endothelial cells have been recapitulated under physiologic flow conditions (Brown et al., 1999; Larson et al., 1997). Upregulation of LFA-1 activity on APL cells after retinoic acid treatment results in APL cell binding to and transmigration through endothelium, analogous to the organ infiltration seen in APL patients being treated with retinoic acid. mAbs against LFA-1 and ICAM-1 completely inhibit the binding to and transmigration through endothelium. Hence, inhibition of LFA-1/ICAM interaction in patients with APL being treated with retinoic acid may protect against the development of retinoic acid syndrome. LFA-1/ICAM inhibition is also applicable to the use of alternatives to retinoic acid, such as 9-cis-retinoic acid or various synthetic retinoids, in APL treatment, to the extent that they cause retinoic acid syndrome.
[0037] Inhibition of the LFA-1 and ICAM-1 binding has potential therapeutic benefits relating to blocking allograft rejection allografts, including cardiac, renal and thryoid allografts (Isobe et al., 1992; Stepkowski et al., 1994; Cosimi et al., 1990; Nakakura et al., 1993; Talento et al., 1993), bone marrow transplants (Tibbetts et al., 1999; Cavazzana-Calvo et al., 1995) T-cell mediated sensitization reactions (Ma et al., 1994; Cumberbatch et al., 1992), diabetes (Hasegawa et al., 1994) and rheumatoid arthritis (Davis et al., 1995; Kavanaugh et al., 1994). Expression of ICAM-1 by keratinocytes is also implicated in the etiology of psoriasis, and inhibition of LFA-1/ICAM-1 binding presents a possible point of therapeutic intervention (Servitje et al., 1996). Thus the peptide compositions of the present invention may be used in treatment of the above conditions and more generally in any condition T-cell mediated condition wherein T-cells are activated via interaction of LFA-1 and ICAM-1.
[0038] The present disclosure provides novel peptide containing compositions that inhibit the LFA-1/ICAM-1 interaction. Preferred are compositions including nine amino acid peptides in which the terminal amino acids are cysteines, thus allowing the peptide to exist in a heterodetic cyclic form by disulfide bond formation or in a homodetic form by amide peptide bond formation between the terminal amino acids. Cyclizing small peptides through disulfide or amide bonds between the N- and C-terminus cysteines may circumvent problems of affinity and half-life. Disulfide bonds connecting the amino and carboxy terminus decrease proteolysis and also increase the rigidity of the structure, which may yield higher affinity compounds. Peptides cyclized by disulfide bonds have free amino- and carboxy-termini which still may be susceptible to proteolytic degradation, while peptides cyclized by formation of an amide bond between the N-terminal amine and C-terminal carboxyl, no longer contain free amino or carboxy termini. Cyclic peptides may have longer half-lives in serum (Picker and Butcher, 1992; Huang et al., 1997). Moreover, the side-effects from peptide therapy are minimal, since anaphylaxis and immune responses against the small peptide occur only rarely (Ohman et al., 1995; Adgey, 1998). Finally cyclic peptides have been shown to be effective inhibitors in vivo of integrins involved in human and animal disease (Jackson et al., 1997; Cuthbertson et al., 1997; Leficovis and Topol, 1995; Goligorsky et al., 1998; Ojima et al., 1995; Noiri et al., 1994). Thus the peptides of the present invention, including CLLRMRSIC (SEQ ID NO: 1), CLLRMRSAC (SEQ ID NO: 40), CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), and CLLRMRSVC (SEQ ID NO: 48), can be linked either by a C-N linkage or a disulfide linkage.
[0039] The present invention is not limited by the method of cyclization of peptides, but encompasses peptides whose cyclic structure may be achieved by any suitable method of synthesis. Thus, heterodetic linkages may include, but are not limited to formation via disulfide, alkylene or sulfide bridges. Methods of synthesis of cyclic homodetic peptides and cyclic heterodetic peptides, including disulfide, sulfide and alkylene bridges, are disclosed in U.S. Pat. No. 5,643,872, herein incorporated in entirety by reference. Other examples of cyclization methods are discussed and disclosed in U.S. Pat. No. 6,008,058, herein incorporated in entirety by reference. Cyclic peptides can also be prepared by incorporation of a type II′ β-turn dipeptide (Doyle et al., 1996). In certain aspects, embodiments of the present invention include cyclic peptides comprising the heptapeptides represented by residues 2 through 8 of the exemplified cysteine-containing nonapeptides. Thus, embodiments of the present invention include cyclic peptides comprising the heptapeptide sequences LLRMRSI (SEQ ID NO: 49), LLRMRSA (SEQ ID NO: 50), LIRMRSA (SEQ ID NO: 51), LLKMRSA (SEQ ID NO: 52), LLRMKSA (SEQ ID NO: 53), ILRMRSA (SEQ ID NO: 54) and LLRMRSV (SEQ ID NO: 55). Peptides that comprise the heptapeptide sequences of the present invention may be a peptide of 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14, or 15 amino acids in length, wherein additional amino acids may be any L-series or any D-series amino acid.
[0040] Phage Display and Consensus Sequence
[0041] As a part of the present disclosure, phage display has been used to identify peptide sequences that bind ICAM-1 and block LFA-1/ICAM interaction. Briefly a library of cysteine-constrained heptapeptides was purchased from New England Labs (Cambridge, Mass.) and screened for its ability to bind the LFA-1 ligand, ICAM-1. Human ICAM-1 has been previously isolated in functional form (Larson et al., 1990), and a variation of this technique was used to obtain purified recombinant soluble ICAM-1 for use in phage display. Each phage in the library has the potential to display a unique cyclic heptapeptide fused to its gene III coat on its surface. The linkage of the displayed random peptide with a phage surface protein forms the basis of the technique. The library consists of approximately 2.8×10 11 random heptapeptide sequences expressed on phage, compared to 20 7 (20 possible amino acids in 7 different positions) or 1.28×10 9 possible heptapeptide sequences. The phage were then screened for their ability to bind purified ICAM-1 by interaction with the displayed heptapeptide sequences. The phage were then screened for their ability to bind purified ICAM-1 by panning (FIG. 2). Bound phage is eluted using the anti-ICAM-1 mAb 84h410. This mAb binds to amino acid residues on ICAM-1 that are similar to those to which LFA-1 binds (Staunton et al., 1990). Elution with R6.5 allowed for isolation of phage expressing cyclic peptides that bind a region on ICAM-1 that is shared with LFA-1 binding. In addition, phage were eluted with mAb for 1 hour so that the peptides with highest affinity and slower off-rates (i.e., peptides most likely to be potent in vivo inhibitors) would be included. Thus, peptide sequences that block ICAM-1/LFA-1 interactions are identified.
[0042] Adherent phage were selected and amplified in ER2537 bacteria through four rounds of panning. The sequences of 12-18 phage in each round were determined. A working consensus peptide was determined after nucleotide sequencing of 18 phage in the fourth and final round (Table 1). Amino acids that were recurring but occurred at lower frequency and did not fit into the consensus sequence are also shown below. The recurring amino acids form the basis of derivative structures. The ability of each phage isolated after four rounds of panning to specifically bind ICAM-1 was also determined in an ELISA assay with serial dilutions of phage.
TABLE 1 PEPTIDE SEQUENCES EXPRESSED ON PHAGE THAT BIND ICAM-1 Amino acid position 1 2 3 4 5 6 7 8 9 Consensus C L L R M R S I C (SEQ ID NO: 1)* Recurring amino acids M P N L R
[0043] The following techniques have been developed or modified for use in the present examples described below.
[0044] Rapid Aggregation Assay for Screening Peptide Effectiveness.
[0045] LFA-1 dependent cell aggregation has been previously studied using an aggregation assay it with a variety of leukocyte subclasses and cell lines (Larson et al., 1990; Wang et al., 1988; Larson et al., 1997). JY cells were obtained form American Type Tissue Culture Collection and were maintained in RPMI 1640 supplemented with 10% FBS at 37° C. in 5% CO 2 . Aggregation of cells was measured in a homotypic aggregation assay using ICAM-1 as a stimuli. JY cells were washed twice with serum free medium and resuspended at a concentration of 4×105 is cells/ml. Cells were preincubated with the desired concentration of peptide for 15 min at room temperature. In a final volume of 100 μl, 50 μl of cells and peptide were seeded in 96 well flat bottomed microtiter plates. Cells were allowed to aggregate at 37° C. in humidified air with 5% CO 2 . Cells were visualized and counted by inverted phase contrast microscopy at the time indicated. Within each well of aggregates as well as the total number of free (single) cells were counted. percent aggregation was determined by the following equation:
Percent aggregation=100×(1−number of free cells/total number of cells)
[0046] Assay for Measuring LFA-1 Dependent Ex Vivo Survival of Leukemic Cells.
[0047] A co-culture assay has been developed by the present inventor that quantifies ex vivo survival of T-ALL cells (Winter et al., 1998). Using this assay, survival of T-ALL cell lines as well as T-ALL cells isolated from patients required LFA-1 binding to ICAM-1 on bone marrow (BM) derived stromal cells. In this assay cryopreserved or fresh leukemic samples are seeded onto HS5 stromal cell monolayers in 24 well plates. The stromal cell line HS5 has been previously shown to support complete hematopoiesis of normal precursor cells (Roecklein and Torak-Storb, 1995). HS5 cells are γ-irradiated with 2500 cGy, a dose that has been determined to prevent stromal cell proliferation over 168 hours. Leukemia cells are harvested at 1 and 96 hours. The number of leukemic cells recovered is measured in a flow cytometer by techniques based on those known in the art (Manabe et al., 1992; Manabe et al., 1994). The leukemia cells are stained by direct immunofluorescence using a fluoroisothiocyanate (FITC) labeled mAb directed against a pan T-ALL antigen CD5 as described (Larson et al., Leukocyte Typing, 1990; Larson and McCurley, 1995). A gate is set around the area of light scatter where the viable CD5 positive T-ALL cells are found at the beginning of the cultures. Then, the T-ALL cells with predetermined light scattering and CD5 presentation are enumerated by counting the number of events passing through the gate in a 60 second time period. In each analysis 5×10 5 fluorescent Immuno-Chek beads (Coulter, Hialeah, Fla.) are added to each sample. The number of beads that pass through the flow cytometer in 60 seconds is also counted, allowing the measured bead number to serve as an internal control for the volume that passes through the flow cytometer in 60 seconds. The calculation is as follows: (number of CD5 T-ALL cells/volume passed through flow cytometer as determined by fluorescent beads)×volume of the sample=the number of cells in the sample. The percentage of survival is calculated by: (number of cells in test sample at t−96 h/number of cell in sample at t−1 h)×100.
[0048] Parallel Plate Flow Chamber for Measuring Leukocyte-Endothelial Cell Interaction under Physiologic Flow Conditions In Vivo.
[0049] An assay has been developed that provides an in vitro model of neutrophils or APL cells binding to activated endothelium. The binding of APL cells using a parallel plate flow chamber recapitulates events that occur in retinoic acid syndrome (Larson et al., 1997; Brown et al., 1999). A parallel plate flow chamber simulates the physiologic flow conditions in blood and adhesive interactions in post-capillary venules. Post-capillary venules are the physiologically relevant locations of leukemia cell-endothelial cell interaction and extravasation. Since parallel plate flow chamber experiments have been shown to accurately recapitulate in vivo observations, a parallel plate flow chamber is used to examine the inhibitory effects of peptides on APL cell line binding and transmigration through endothelium under physiologic flow conditions. Monolayers of endothelial cells are placed in the parallel plate flow chamber, and the leukemic cells are pumped through the chamber at physiologic flow rates. The interaction between the flowing leukemia cells and the endothelium are videotaped microscopically, and the number of rolling, firmly adhered and transmigrated leukemia cells is quantified by computer-assisted image analysis.
[0050] With all-trans retinoic acid (ATRA) treatment, the APL cell line NB-4 acquires the ability to firmly attach to activated endothelium via LFA-1/ICAM-1 interaction. Inhibition of LFA-1/ICAM-1 interaction prevents firm adherence to and transmigration through endothelium of the APL cell line under physiologic flow. This has been demonstrated with monoclonal antibodies against LFA-1 and ICAM-1, which prevent firm attachment to and transmigration through activated endothelium of APL cells in a parallel plate flow chamber (Larson et al., 1997; Brown et al, 1999). Flowing ATRA-treated APL cell lines over activated endothelial cell monolayers in a parallel flow chamber determines the effectiveness of peptides to inhibit LFA-1 dependent firm adherence and subsequent transmigration under physiologic flow conditions. ICAM-1 expressed on activated endothelial monolayers are incubated with cyclic peptides over a range of concentrations (10 −4 to 10 −8 M) and the IC 50 is determined.
[0051] For investigating neutrophil binding, neutrophils are isolated from heparin anticoagulated venous blood of healthy adult donors by centrifugation on Ficoll-Hypaque density gradients as described by Simon et al. (1992). Isolated neutrophils are suspended at a concentration of 10 7 /ml in Hanks' Balanced Salt Solution supplemented with 10 mmol/L HEPES, pH 7.4 and 0.2% human serum albumin (Armour Pharmaceutical, Kankakee, Ill.) and used within 2 hours of preparation. Neutrophils are kept on ice and resuspended in RPMi pre-warmed to 37° C. immediately before use.
[0052] Monoclonal Antibodies
[0053] In order to have adequate monoclonal antibodies at a reasonable cost, hybridomas were grown by the present inventor and mAbs were purified for blocking studies. The following monoclonal antibodies have been isolated from hybridoma supernatants: mAbs against LFA-1 (TS2/4 and TSI/22) and ICAM-1 (RRI/1, R6.5 and 84H10) (Larson et al, 1997).
[0054] Screening Assay
[0055] The ability of candidate compounds to bind to ICAM-1 is assessed by a competitive binding assay. Candidate compounds may be peptide or non-peptide compounds. Binding to ICAM-1 is quantified by the ability to displace a peptide of the present invention, including the peptides CLLRMRSIC (SEQ ID NO: 1), CLLRMRSAC (SEQ ID NO: 40), CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), and CLLRMRSVC (SEQ ID NO: 48), from ICAM-1. The displaced peptide can be assayed by a number of techniques. For example, radiolabeled peptide can be synthesized using commercial available radiolabeled amino acids precursors. Peptides radiolabelled with H 3 , C 14 or S 35 can be quantified by routine liquid scintillation techniques. Alternatively, a fluorescent labeled peptide can be synthesized. For example, lysine can be inserted in a non-critical position and labeled with fluroescein isothiocyanate (“FITC”). In addition to FITC, the peptide may be labeled with any suitable flurophore. A carboxy fluroescein derivative of SEQ ID NO: 1 has been prepared. The 5(6)-carboxy fluorescein derivative of the disulfide constrained cyclic form of SEQ ID NO: 40, as shown by FIG. 3, has been synthesized by Biopeptide (San Deiego, Calif.): Alternatively, peptides cyclized with an amide peptide linkage have free sulfhydryl groups available for linkage to fluorescent compounds such as thiocyanates. Separation of bound from unbound peptide and quantitation of displaced peptide can be performed by routine techniques known to one of skill in the art. This embodiment of the invention is not limited by the method used to quantify the displaced peptide, and any suitable analytical technique may be used and be within the scope of the invention.
[0056] The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
EXAMPLE 1
Consensus Sequence Peptide Blocks LFA-1/1CAM-1 Dependent Cell Aggregation
[0057] The consensus peptide (SEQ ID NO: 1) and the randomized sequence CLMIRMLRC (SEQ ID NO: 33), cyclizied in the disulfide-linked form, were synthesized by Biopeptide (San Diego, Calif.) and tested in a screening assay for the ability to inhibit aggregation of the cell line JY, which aggregates in an LFA-1/CAM-1 dependent manner. Aggregation measurements are relatively rapid and quantifiable. Furthermore, small volumes are used minimizing peptide consumption. Finally, cell aggregation in vitro depends on a multivalent LFA-1/ICAM-1 interaction. A peptide that is identified as being able to block cell aggregation in vitro is, therefore, likely to have affinity and off-rate characteristics that would make it an effective in vivo inhibitor, since cell-cell interaction in vivo also involves multivalent LFA-1 /ICAM-1 interaction. Using this assay, the consensus peptide sequence has an IC 50 of 500 μM (FIG. 1).
EXAMPLE 2
Derivative Peptide Antagonists
[0058] The consensus peptide sequence (SEQ ID NO: 1) identified by phage display and described in Example 1 has an IC 50 Of 800 μM for cell aggregation and 250 nM for monovalent ICAM binding. Monovalent ICAM-1 binding is measured by standard ELISA techniques, wherein, for example, the inhibition of 84H10 binding to ICAM-1 is assayed. For in vivo use, preferred peptides would have IC 50 's of about 10 μM to 800 μM for cell aggregation and from about 10 to 250 nM for monovalent ICAM binding. In order to obtain more effective inhibitory peptides, standard techniques of designing derivative structures may be used to produce candidates to be tested for enhanced inhibitory capacity. This strategy has been shown to be effective in developing in vivo peptide inhibitors to other adhesion molecules (Ohman et al., 1995; Adgey, 1998).
[0059] For example, heptapeptide sequences are proposed on the basis of the observed consensus sequence of different phage sequences that were discovered in the phage display studies described above. Two of the amino acid positions in the consensus sequence show greater than 80% identity among phage and therefore are fixed (positions 3 and 4 of Table 1). The other positions are altered using 1 of 2 possible amino acids as shown in Table 2. The amino acids employed in the altered positions are identical to the recurring amino acids identified by phage display, but are represented at too low a frequency to be incorporated in the consensus sequence peptide. Using these combinations, 32 cysteine restrained heptapeptides are available as candidate inhibitors.
[0060] Peptides are initially tested for their ability to block LFA-1/ICAM dependent aggregation of the cell line JY (Wang et al., 1988; Larson et al., 1997). Peptides are preferably tested over a range of concentrations (10 1 to 10 8 μM, for example) and the concentration leading to half maximal inhibition of aggregation (IC50) is determined for all the peptide sequences.
TABLE 2 Peptide Antagonists Identified by Phage Display No. Sequence No. Sequence SEQ ID NO: 1 CLLRMRSIC SEQ ID NO: 17 CMLRMRSIC SEQ ID NO: 2 CLLRMRSRC SEQ ID NO: 18 CMLRMRSRC SEQ ID NO: 3 CLLRMRLIC SEQ ID NO: 19 CMLRMRLIC SEQ ID NO: 4 CLLRMRLRC SEQ ID NO: 20 CMLRMRLRC SEQ ID NO: 5 CLLRPRSIC SEQ ID NO: 21 CMLRPRSIC SEQ ID NO: 6 CLLRPRSRC SEQ ID NO: 22 CMLRPRSRC SEQ ID NO: 7 CLLRPRLIC SEQ ID NO: 23 CMLRPRLIC SEQ ID NO: 8 CLLRPRLRC SEQ ID NO: 24 CMLRPRLRC SEQ ID NO: 9 CLLRMNSIC SEQ ID NO: 25 CMLRMNSIC SEQ ID NO: 10 CLLRMNSRC SEQ ID NO: 26 CMLRMNSRC SEQ ID NO: 11 CLLRMNLIC SEQ ID NO: 27 CMLRMNLIC SEQ ID NO: 12 CLLRMNLRC SEQ ID NO: 28 CMLRMNLRC SEQ ID NO: 13 CLLRPNSIC SEQ ID NO: 29 CMLRPNSIC SEQ ID NO: 14 CLLRPNSRC SEQ ID NO: 30 CMLRPNSRC SEQ ID NO: 15 CLLRPNLIC SEQ ID NO: 31 CMLRPNLIC SEQ ID NO: 16 CLLRPNLRC SEQ ID NO: 32 CMLRPNLRC
[0061] Alanine Screen of Consensus Sequence
[0062] An alternative derivative peptide strategy was undertaken in which the consensus sequence peptide was subjected to an alanine-screening procedure as described by Cunningham and Wells, 1989. Peptides cyclizied in the disulfide-linked form were synthesized by Biopeptide (San Diego, Calif.) wherein an alanine was substituted at each position in the hepatapeptide LLRMRSI of the consensus sequence SEQ ID NO: 1, and each peptide was examined in parallel for its ability to inhibit LFA-1/ICAM-1 mediated JY cell aggregation. The results are shown in Table 2. Six of the seven peptides were soluble in aqueous solution. SEQ ID NO: 376, representing a substitution of the arginine in position 4 of SEQ ID NO: 1, was not soluble at 1 nm and could not be tested. Loss of inhibitory function resulted from alanine substitution of the leucines in positions 2 (SEQ ID NO: 34) and 3 (SEQ ID NO: 35), methionine in position 5 (SEQ ID NO: 36), and arginine in position 6 (SEQ ID NO: 38) of SEQ ID NO: 1, indicating that these amino acids are important to the antagonistic activity of the peptide. Substitution of the serine in position 7 (SEQ ID NO: 39) had no significant effect on the inhibitory activity of the peptide. Alanine substitution of the isoleucine at position 8 of SEQ ID NO: 1, i.e., CLLRMRSAC (SEQ ID NO: 40), resulted in a more potent antagonist. The randomized sequence CLRLSRIMC (SEQ ID NO: 56) was used as a control. This randomized sequence has a greater aqueous solubility than the alternative randomized sequence CLMIRMLRC (SEQ ID NO: 33). Conservative substitutions in other peptide antagonists been shown to result in more potent inhibitors (Jennings and White, 1998).
TABLE 3 Inhibition of JY cell aggregation with alanine-substituted derivations Percent JY SEQ ID NO: Sequence Aggregation Percent Inhibition No Peptide 76(12) 0(16) SEQ ID NO: 56* CLRLSRIMC 74(14) 4(18) SEQ ID NO: 1 CLLRMRSIC 41(8) 46(11) SEQ ID NO: 34 CALRMRSIC 71(15) 7(19) SEQ ID NO: 35 CLARMRSIC 69(17) 9(22) SEQ ID NO: 36 CLLAMRSIC Not Soluble Not Soluble SEQ ID NO: 37 CLLRARSIC 72(11) 5(14) SEQ ID NO: 38 CLLRMASIC 68(9) 11(12) SEQ ID NO: 39 CLLRMRAIC 56(16) 27(21) SEQ ID NO: 40 CLLRMRSAC 29(13) 61(17)
[0063] Conservative Subtitutions of Amino Acids
[0064] The important amino acids of SEQ ID NO: 40, as identified by the alanine substitutions, were substituted with amino acids of like charge, e.g., as described by Dayoff et al., Atlas of Protein Sequence and Structure; vol 5, Suppl. 3, pp3,45-362 (M. O. Dayoff, ed., Nat'l BioMed Research Fdn., Washington, D.C. 1979). Peptides cyclizied in the disulfide-linked form were synthesized by Biopeptide (San Diego, Calif.) and were examined for their ability to inhibit LFA-1/ICAM-1 mediated JY cell aggregation. The results are summarized in Table 4. Five peptide sequences exhibited greater inhibition of JY cell inhibition as compared to SEQ ID NO: 1, i.e., CILRMRSAC (SEQ ID NO: 43), CLIRMRSAC (SEQ ID NO: 44), CLLKMRSAC (SEQ ID NO: 45), CLLRMKSAC (SEQ ID NO: 46), and CLLRMRSVC (SEQ ID NO: 48). This type of derivative strategy has previously been shown to be successful at identifying higher affinity peptides (Ohman et al., 1995; Adgey, 1998). In addition to binding to ICAM, conservative varaints can also be screened for other desirable properties such as a longer serum-half life or desirable other pharmacokinetic of pharnacodymanic properties.
TABLE 4 Inhibition of JY cell aggregation with homologous amino acid substitutions Percent JY SEQ ID NO: Sequence Aggregation Percent Inhibition No Peptide 55(3) 0(5) SEQ ID NO: 56* CLRLSRIMC 57(4) −3.6(7) SEQ ID NO: 1 CLLRMRSIC 30(5) 45(9) SEQ ID NO: 41 CLVRMRSAC 55(1) 0(1) SEQ ID NO: 42 CVLRMRSAC 24(3) 56(6) SEQ ID NO: 43 CILRMRSAC 4(5) 92(9) SEQ ID NO: 44 CLIRMRSAC 4(2) 93(3) SEQ ID NO: 45 CLLKMRSAC 3(2) 94(3) SEQ ID NO: 46 CLLRMKSAC 6(2) 90(4) SEQ ID NO: 47 CLLRMRSLC 61(7) −12(13) SEQ ID NO: 48 CLLRMRSVC 4(1) 92(3)
EXAMPLE 3
Investigation Of Peptide Inhibition Of LFA-1/ICAM-1 Interaction
[0065] The cyclic peptide inhibitors having the amino acid sequences, CLLRMRSIC (SEQ ID NO: 1) and CLLRMKSAC (SEQ ID NO: 46) have been shown to block neutrophil-binding to endothelium under physiologic flow conditions in a parallel plate flow chamber. The data is shown in Table 5. In similar fashion to the inhibition of JY cell aggregation, SEQ ID NO: 46 exhibited greater inhibition of attachment of neutrophils to activated endothelium.
TABLE 5 Inhibition of Firm Attachment of Neutrophils to Stimulated Endothelial Cells in a Parallel Plate Flow Chamber SEQ ID NO: Sequence Cells/mm 2 Percent Inhibition No Peptide 821(96) 0(12) SEQ ID NO: 56* CLRLSRIMC 617(152) 25(19) SEQ ID NO: 1 CLLRMRSIC 439(120) 47(15) SEQ ID NO: 46 CLLRMKSAC 283(0) 66(0)
[0066] The peptides of the present invention bind to ICAM-1 and block cell-cell adhesion that is dependent on LFA-1 binding to its ligand, ICAM-1. In contrast to other peptide inhibitors, these compounds have no structural similarity to fragments or portions of LFA-1 or ICAM-1. These compound are, therefore, effective agents in the treatment of myocardial infarction, rheumatoid arthritis, asthma, and leukemia/lymphoma, and are contemplated to be especially effective in adjunct therapy of acute T-ALL and retinoic acid syndrome in APL.
[0067] Regarding the clinical utility of the disclosed compositions, preliminary data indicate that approximately 80% of cases of T-ALL may utilize LFA-1 dependent adhesion for survival. Therefore, the peptide inhibitor may be useful in 80% of cases of T-ALL when incorporated as adjunct therapy. Side effects related to use of a small peptide are contemplated to be minimal, since peptidomimetics inhibiting other integrin functions, and now in clinical trial do not have significant side-effects (Ohman et al., 1995; Adgey, 1998). However, LFA-1 may be critical to an aspect of hematopoiesis that is as yet undefined.
[0068] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are chemically or physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
1
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Cys Leu Leu Arg Met Arg Ser Arg Cys
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Cys Leu Leu Arg Met Arg Leu Ile Cys
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Cys Leu Leu Arg Met Arg Ser Ile Cys
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Cys Leu Leu Arg Met Arg Leu Arg Cys
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Cys Leu Leu Arg Pro Arg Ser Ile Cys
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Cys Leu Leu Arg Pro Arg Ser Arg Cys
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Cys Leu Leu Arg Pro Arg Leu Ile Cys
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Cys Leu Leu Arg Pro Arg Leu Arg Cys
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Cys Leu Leu Arg Met Asn Ser Ile Cys
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Cys Leu Leu Arg Met Asn Ser Arg Cys
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Cys Leu Leu Arg Met Asn Leu Ile Cys
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Cys Leu Leu Arg Met Asn Leu Arg Cys
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Cys Leu Leu Arg Pro Asn Ser Ile Cys
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Cys Leu Leu Arg Pro Asn Ser Arg Cys
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Cys Leu Leu Arg Pro Asn Leu Ile Cys
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Cys Leu Leu Arg Pro Asn Leu Arg Cys
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Cys Met Leu Arg Met Arg Ser Ile Cys
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Cys Met Leu Arg Met Arg Ser Arg Cys
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Cys Met Leu Arg Met Arg Leu Ile Cys
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Cys Met Leu Arg Met Arg Leu Arg Cys
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Cys Met Leu Arg Pro Arg Ser Ile Cys
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Cys Met Leu Arg Pro Arg Ser Arg Cys
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Cys Met Leu Arg Pro Arg Leu Ile Cys
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Cys Met Leu Arg Pro Arg Leu Arg Cys
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Cys Met Leu Arg Met Asn Ser Ile Cys
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Cys Met Leu Arg Met Asn Ser Arg Cys
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Cys Met Leu Arg Met Asn Leu Ile Cys
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Cys Met Leu Arg Met Asn Leu Arg Cys
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Cys Met Leu Arg Pro Asn Ser Ile Cys
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Cys Met Leu Arg Pro Asn Ser Arg Cys
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31
Cys Met Leu Arg Pro Asn Leu Ile Cys
1 5
32
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Cys Met Leu Arg Pro Asn Leu Arg Cys
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33
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33
Cys Leu Met Ile Arg Met Leu Arg Cys
1 5
34
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34
Cys Ala Leu Arg Met Arg Ser Ile Cys
1 5
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Cys Leu Ala Arg Met Arg Ser Ile Cys
1 5
36
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Cys Leu Leu Ala Met Arg Ser Ile Cys
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Cys Leu Leu Arg Ala Arg Ser Ile Cys
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Cys Leu Leu Arg Met Ala Ser Ile Cys
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Cys Leu Leu Arg Met Arg Ala Ile Cys
1 5
40
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40
Cys Leu Leu Arg Met Arg Ser Ala Cys
1 5
41
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Cys Leu Val Arg Met Arg Ser Ala Cys
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Cys Val Leu Arg Met Arg Ser Ala Cys
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43
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Cys Ile Leu Arg Met Arg Ser Ala Cys
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44
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Cys Leu Ile Arg Met Arg Ser Ala Cys
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45
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45
Cys Leu Leu Lys Met Arg Ser Ala Cys
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46
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46
Cys Leu Leu Arg Met Lys Ser Ala Cys
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Cys Leu Leu Arg Met Arg Ser Leu Cys
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48
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48
Cys Leu Leu Arg Met Arg Ser Val Cys
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49
7
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49
Leu Leu Arg Met Arg Ser Ile
1 5
50
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50
Leu Leu Arg Met Arg Ser Ala
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51
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Leu Ile Arg Met Arg Ser Ala
1 5
52
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Leu Leu Lys Met Arg Ser Ala
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53
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Leu Leu Arg Met Lys Ser Ala
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54
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54
Ile Leu Arg Met Arg Ser Ala
1 5
55
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Leu Leu Arg Met Arg Ser Val
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Cys Leu Arg Leu Ser Arg Ile Met Cys
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Cyclic peptides inhibit LFA-1 interaction with ICAM-1 and are useful in treatment of hematopoietic neoplasms and in adjunct therapy in prevention of retinoic acid syndrome and diseases involving emigration of leukocytes into organ tissue.
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RELATED APPLICATIONS
This application is a continuation in part of application Ser. No. 10/601,046 filed Jun. 21, 2003 now U.S. Pat. No. 7,036,285, which is a continuation of application Ser. No. 10/022,612 filed Dec. 18, 2001 now U.S. Pat. No. 6,581,348, which claims benefit from provisional application Ser. No. 60/298,517 filed Jun. 15, 2001.
FIELD OF THE INVENTION
The present invention relates to roofing systems.
BACKGROUND OF THE INVENTION
Rigid foam panels for providing a roofing membrane layer are currently available for use as an insulating underlayment in roof construction. Typically these are 4′ by 8′ (1.22 m by 2.44 m) panels 1.5″ (3.8 cm) thick made of a 1.6 pound per cubic foot polyurethane foam with a tar paper top layer. Such a material is not crush resistant enough to be used as a roof surface material and can also be easily punctured.
Core panels are common in the art and may be used in conjunction with a roof membrane layer. The functions of core panels include providing a fireproofing layer; providing a thermal barrier; providing a solvent barrier or moisture barrier; and providing an air barrier. One form of core paneling is a fiberglass-faced asphaltic board. Asphaltic boards are known to provide adequate moisture resistance, but may not serve as a fire barrier.
A second type of core panel is a semi-rigid rock wool or fiberglass. Boards of this type are permeable to moisture, provide little impact resistance, and do not provide a fire barrier.
A third type of core panel known in the art is a plywood, or veneer, sheet. Veneer sheets are combustible, however. Further, plywood sheets lose strength when wet, yet provide adequate strength for foot traffic.
A fourth type of core panel is a wood fiberboard, comprising organic fibers bonded with resin. Fiberboard is also combustible and loses strength when wet. Fiberboard provides at least some foot traffic protection, but crumbles when wet.
A fifth type of core panel is perlite, comprising a mineral aggregate board with cellulose binders and sizing agents. A perlite core panel may be used as a fire barrier. However, perlite core panels may fall apart when wet and are crushed by foot traffic.
A sixth type of core panel is a panel comprising a gypsum core with paper facers on each side. Paper-faced gypsum boards may be used in fire protection and provide moderate resistance to foot traffic. However, the paper facers may delaminate when wet.
In addition to the common type of core panels mentioned above, improved core panels exist providing properties specific to use. One example of an improved core panel is the Dens-Deck® Roof Board. This Roof Board comprises a high-density gypsum core and fiberglass mats embedded on both sides. The Roof Board may include a fireproofing layer, which may be as thin as ¼ inch. Such core panels may neither delaminate with moisture nor support mold growth. Furthermore, Roof Boards may support foot traffic and resist hail.
More specifically, core panels as described herein serve to support a roofing membrane and may be structurally located beneath a roofing membrane. The roofing membrane may adhere to the Dens-Deck® Roof Board directly. Typically, the edges of the Dens-Deck Roof Board should be butted together. However, for the condition of high gain in surface temperature, slight gaps may be required.
Optionally, a separating material may be used between the core panel and the roofing membrane. Further, several methods known in the art may be utilized to bond the separated core panels. One such method is known as “hot-mopping.” A second method of bonding core panels is known as “torching.” Torching may involve the application of a bitumen membrane, such as a “Dibiter APP modified bitumen member,” atop the core panels. The bitumen membrane, or “flashing member,” may then be positioned by the application of a heat-welding technique.
OBJECTS OF THE INVENTION
It is therefore an object of the present invention to provide a sturdy, weatherproof seamless roofing system that uses rigid foam boards or panels to create a seamless waterproof roof.
SUMMARY OF THE INVENTION
The roofing panels of this invention differ from the prior art underlayment product in several respects. The panels of this invention are:
a) made of a denser polyurethane foam (approximately 3 pounds per cubic foot) and, b) include an integral top layer of non-woven 250 gram polyester fabric that is saturated by the foam during manufacture by the laminator in a controlled factory environment.
The higher density affords more crush resistance, while the well bonded top layer resists punctures and provides a better adhesion surface for elastomeric top coats.
The roofing panels are bonded to roof substrate with low rise foam polyurethane adhesive which seeps through loose tongue-in-groove joints to form a blob at the top, which is shaved off and covered with a fabric top layer.
After the adhesive cures, a very secure bond between the panels results.
The low-rise foam adhesive is a two-part mixture that has distinct phases after mixing. By varying the formulations of the two parts, the “cream time” (i.e.—to achieve the consistency of shaving cream) as well as the “tack free” time can be controlled.
The panels are placed on the foam just after cream consistency and well before tack-free time so that the foam rises through the joints. After the adhesive cures to a solid consistency, the blobs are removed from all of the joints. This is typically accomplished by grinding using a disk pad grinder.
The roof is finished by applying a layer of waterproof elastomeric coating which covers the entire surface creating a monolithic structure.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention can best be understand in connection with the accompanying drawings, in which:
FIG. 1 is a top plan view of a roof section; showing outlines of roofing panels of this invention;
FIG. 2 is a top plan view of an embodiment for a tongue-in-groove roofing panel of this invention;
FIG. 3 is an edge cross-section detail view of further embodiment for an all-groove panel of this invention with an insertable tongue board;
FIG. 4 is an edge cross-section view of yet another embodiment for tongue-in-groove roofing panels of this invention, shown adhesively bonded to a roof substrate;
FIG. 5 is an edge cross-section detail view of a still further alternate embodiment of this invention, shown with a ship-lap joint configuration;
FIG. 6 is an edge cross-section detail view showing a panel joint of this invention in a finished roof section;
FIG. 7 is a high level flow chart of the roofing system method of this invention;
FIG. 8 is a roof edge detail view in cross-section, illustrating flashing and interfacing to the roofing system of this invention;
FIG. 9 is a perspective cutaway view, detailing the layering of a fireproof roofing system having a corrugated roof deck;
FIG. 10 is a side elevational cutaway view thereof, detailing the incorporated layers of a fireproof gypsum layer;
FIG. 11 is a perspective view of a rolled conventional multi-ply sheet of bitumen compound material for use with the roofing system according to another fireproof embodiment of the current invention.
FIG. 12 is a cross-sectional view of a fireproof roofing system according to an embodiment of the current invention further utilizing the rolled conventional multi-ply sheet of bitumen compound material of FIG. 11 .
DETAILED DESCRIPTION OF THE INVENTION
The roofing system of this invention uses rigid foam boards or panels to create a seamless waterproof roof. It can be used over a number of different substrates including metal decking, tar and gravel, or polyurethane foam in new construction as well as re-roofing applications.
Rigid foam panels are currently available for use as insulating underlayment in roof construction. Typically these are 4′ by 8′ (1.22 m by 2.44 m) panels 1.5′″ (3.8 cm) thick made of a 1.6 pound per cubic foot polyurethane foam with a tar paper top layer. Such a material is not crush resistant enough to be used as a roof surface material and can also be easily punctured.
The roofing panels of this invention differ from this underlayment product in several respects. Although panel size as well as material are similar, the panels of this invention are made of a denser polyurethane foam (approximately 3 pounds per cubic foot) and include an integral top layer of non-woven 250 gram polyester fabric that is saturated by the foam during manufacture by the laminator in a controlled factory environment. The higher density affords more crush resistance, while the well bonded top layer resists punctures and provides a better adhesion surface for elastomeric top coats.
FIG. 1 is a top view of a roof 1 section showing the outline of the individual roof panels. The panel seams are staggered by using alternate whole panels A as well as half panels B at the roof edge 2 . This is done to prevent any tendency for propagation of inadvertent seam separations.
FIG. 2 shows a top view of a tongue-in groove panel 5 , tongue edges 6 and groove edges 7 .
Since a protruding tongue of polyurethane foam could be damaged in transit, an alternate embodiment of a tongue-in groove construction is shown in FIG. 3 . In this all-groove construction, each polyurethane panel 10 has grooves 11 cut in all four edges. A length of polyurethane plank 12 is then inserted in groove 11 on two edges at the work site. Plank 12 is dimensioned as a press fit in groove 11 and protrudes from the edge to form the tongue after insertion. Planks 12 would be shipped separately in protective packaging to the work site.
FIG. 4 is an edge cross-section view of roofing panels 5 bonded to roof substrate 16 with low rise foam polyurethane adhesive 17 which seeps through loose tongue-in-groove joints to form a blob 18 at the top. Factory bonded fabric 15 is a top layer. Typically, the groove 7 is ⅞″ (22 mm) wide while the tongue is ¾″ (19 mm) wide; this affords enough space for the adhesive foam to rise through while affording close line-up of the top surfaces of adjacent boards 5 . After adhesive 17 cures, a very secure bond between panels 5 results.
FIG. 5 is a detail of an alternative panel joint. Here panels 20 have a ship-lap edge which is also dimensioned so as to permit rising foam adhesive to flow through the joint. For ship-lap panels 20 , the order in which they are laid into the foam is important.
As shown in FIG. 5 , panel X should be laid down before panel Y so that there would not be a tendency to lift panel Y during the foam rising phase.
Foam adhesive is a two-part mixture that has distinct phases after mixing. By varying the formulations of the two parts, the “cream time” (i.e.—to achieve the consistency of shaving cream) as well as the “tack free” time can be controlled. For this invention, a cream time of about 1 minute and a tack-free time of about 4 minutes is ideal. The panels are placed on the foam just after cream consistency and well before tack-free time so that the foam rises through the joints.
After the adhesive cures to a solid consistency, the blobs 18 are removed from all of the joints. This is typically accomplished by grinding using a cutter, such as a knife or disk pad grinder. At this stage, the joint is flush with the fabric top surface of the adjacent panels.
The roof is finished by applying a layer of waterproof elastomeric coating which covers the entire surface creating a monolithic structure.
FIG. 6 is a detailed view of a finished joint between two panels 5 after the blob 18 has been removed and elastomeric coating 25 has been applied. Coating 25 can be an acrylic, urethane or silicone material. It can be sprayed or brushed on.
Flow chart 7 is a concise description of the overall installation process. Two people are generally involved as a team. One worker sprays a panel-width line of low rise polyurethane adhesive, while the second worker follows (after the mix is of cream consistency) and lay down panels. As per FIG. 1 , the first panel at an edge is either a full or half panel to create the staggered seam pattern. Only after the entire roof (or large section) is paneled, are the seep-through joint blobs removed. All debris must be removed carefully before a final seal coat is applied.
Penetrations and wall flashings are first sealed with spray foam prior to sealing.
FIG. 8 is a detail at a roof edge showing an end panel 5 interfacing with aluminum edging 30 which bridges wall 31 , beam 29 and foam panel 5 . A V-groove 28 is cut from the corner of panel 5 at the juncture of edging 30 to permit an aluminum surface to be bonded and sealed to the fabric 15 top layer by waterproof coating 25 .
FIG. 9 is a stepped cutaway view of a further embodiment for a fire resistant roof panel 110 having fireproof panel 140 attached thereto, wherein panel 110 with fireproof layer 140 is attached to roof deck 116 by in-situ applied foam layer 117 , which rises through crevices 111 between adjacent panels 110 . FIG. 10 is a side elevational crossectional view thereof.
For example, FIGS. 9 and 10 show first a structural deck 116 (corrugated deck members shown as an example). Above the structural deck 116 is in-situ deposited layer 117 of rising foam, which rises as protruding foam intrusions 118 through the crevice gaps 111 between discrete cured foam panels 110 , similar to the rise of foam protrusions 18 from in-situ base foam layer 17 between panels 10 shown in FIGS.1–6 .
FIGS. 9 and 10 also show the protruding foam 118 also going optionally downward in the indentations of the corrugated structural deck 116 . Such would not happen if panel 110 was applied to a roof deck 16 which was entirely flat, as in FIGS. 4–6 , but would be the case if the rising foam underlayer 117 were applied to a corrugated structural deck 116 . It is anticipated that the fire resistant embodiment shown in FIGS. 9 and 10 can be applied to either a corrugated roof deck 116 or to a flat roof deck 16 , as in FIGS. 4–6 .
The next layer shown in FIGS. 9 and 10 is a fireproof gypsum layer 140 , such as manufactured by DENS-DECK®, adhered to the bottom of the upper discrete panels 110 . Above panels 110 is a mesh layer 115 . Not shown in FIGS. 9 and 10 are the excess globs of risen foam which are shaved off of the tops of rising foam protrusions 118 , as well as the overlay of a waterproof coating outer skin layer 125 above fabric mesh 115 .
FIG. 11 shows an optional rolled conventional multi-ply sheet of bitumen compound material 150 , including slate granule covered upper layer 150 a of a modified bitumen compound, middle polyester reinforcement layer 150 and lower layer 150 c of a modified bitumen compound. Bitumen sheet 150 could be optionally placed adjacent to the fireproof gypsum layer 140 and/or the discrete foam panel 110 .
FIG. 12 is a crossectional cutaway view of another embodiment for a fire resistant roof section, showing the lower in-situ foam layer 117 , with a protruding portion 118 of the foam layer 117 shown having risen vertically up through the recess gap 111 , between adjacent discrete foam panels 110 , having the fireproof gypsum layer 140 attached at a bottom edge thereof.
The gypsum layer 140 shown in FIGS. 11 and 12 may expand or contract under adverse temperature conditions. The risen foam 118 is slightly resilient, so it may squeeze inward slightly, if the gypsum board layer 140 expands under conditions of high gain in surface temperature.
It is further noted that other modifications may be made to the present invention, within the scope of the invention, as noted in the appended Claims.
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A crush resistant seamless roofing system is formed by a layer of adjacent panels having loose joints filled by expanding rising foam adhesive, which is trimmed to remove excess foam adhesive above a top plane of the roofing system. The roofing system thus formed is covered by a fabric layer and a coating. Further, the seamless roofing system is combined with a base layer, located beneath the panels, the base layer comprising bonded panels of a lightweight fireproofing material, resistant to moisture and foot traffic.
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BACKGROUND OF THE INVENTION
This invention relates to the art of organo tin compounds, the art of stabilization of polymers, and the art of polythioethers and polythioformals. Poly(vinyl chloride) is relatively unstable to heat and light. Initiation by heat involves rupture of the carbon-chlorine bond adjacent to a structure such as terminal unsaturation which reduces its stability. Initiation by ultraviolet light which is absorbed at unsaturated structures also results in release of adjacent chlorine atoms. The chlorine radical formed by either initiating event then abstracts hydrogen to form HCl. The chain radical forms chain unsaturation with consequent generation of another chlorine radical. The presence of oxygen accelerates the process and serves to introduce ketonic structures in the chain.
Improvement in the heat and light stability requires the addition of stabilizers. Metallic salts of tin, lead, barium or cadmium are used. Oxides, hydroxides, or fatty acid salts have been commonly considered among the most effective. Dialkyl tin mercaptides particularly those derived from mercapto-acetic and mercaptopropionic esters are known among this group of stablizers.
The present invention provides novel dialkyl or diaryl tin mercapto derivatives which are suitable for use as stabilizers for poly(vinyl chloride).
Applicant is unaware of any art materially relevant to the invention of this application.
SUMMARY OF THE INVENTION
The invention provides in a composition aspect a compound of the formula (I): ##STR1## Wherein R is --(CH 2 ) m --(OCH 2 ) p --O--(CH 2 ) m --(OCH 2 ) p ] n (CH 2 ) m --
Wherein p is 0 or 1, m is 2 to about 6, and n is 0 to about 6; and R' is lower alkyl of up to about 10 carbon atoms, or carbocyclic aryl containing 1 or 2 aromatic rings.
The tangible embodiments of this composition aspect of the invention possess the inherent physical properties of being mobile liquids of low volatility, being substantially insoluble in water and soluble in such common organic solvent as toluene and acetone.
The nature of the starting materials, the mode of synthesis and the resemblance to analogous known materials further confirms the structure assigned the compounds sought to be patented.
The tangible embodiments of this composition aspect of the invention possess the inherent applied use characteristic of being ultraviolet light stabilizers for poly(vinyl chloride).
The invention provides in another composition aspect a light and heat stabilized composition based on poly(vinyl chloride) which comprises:
(a) a poly(vinyl chloride) resin; and
(b) a compound of Formula I.
The invention also provides in a process aspect a process for the preparation of a heat and light stabilized composition based on a poly(vinyl chloride) resin which comprises: blending with a poly(vinyl chloride) resin an effective amount of a compound of Formula I.
Special mention is made of the composition and process aspects of the invention wherein in the tangible embodiments of Formula I p is 1, m is 2, n is 0 and R' is n-butyl.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The manner of making and using the compositions of the invention will now be described with reference to a specific embodiment thereof namely; a typical general purpose poly(vinyl chloride) resin, Geon 103 (supplied by B. F. Goodrich Co.) containing 7,7,17,17-tetrabutyl -1,3,11,13-tetraoxa -6,8,16,18-tetrathia -7,17-di-stannacycloeicosane (Ia). ##STR2##
To prepare this composition the Geon 103, if desired, a plasticizer, conveniently dioctyl phthalate and Ia may be compounded together either on hot rolls or in a hot mixer such as Banbury. Upon cooling the composition, if plasticized, may then be calendered into sheets, films, or floor covering, or it may be extruded for such uses as wire insulation or tubing and hosing. If unplasticized, the compositions may be used in molding applications such as the production of phonograph records.
It will be obvious to one skilled in the art that in place of the Geon 103 poly(vinyl chloride) resin described, any of the commercially available poly(vinyl chloride) resins may be substituted in the aforesaid process to obtain analogous products therefrom. Similarly, if it is desired to employ a plasticizer, other conventional plasticizers such as trioctylphosphate, dioctyl sebacate and adipate and various low molecular weight polymers such as poly(propylene gylcol) esters or even tricresyl phosphate, dibutyl phthalate, dibutyl sebacate, or tributyl phosphate or mixtures thereof may be used in place of or together with dioctylphthalate illustrated. The optimum concentration of such plasticizer will of course vary according to the desired end use, but it will be the amount normally used for such application and it will be readily selected by one skilled in the art. Typically plasticizer may be added up to about 50% of the total composition weight, with about 30% being usual for film and sheeting applications. It will also be obvious that it place of the compound Ia illustrated, one may substitute any of the other compounds contemplated under Formula I to prepare equivalent stabilized compositions.
Ia may be prepared by treating bis (β-chloro-ethyl) formal (II) with sodium hydrosulfide in aqueous solution under hydrogen sulfide gas pressure at ambient temperatures to produce a compound of the formula:
HSCH.sub.2 CH.sub.2 OCH.sub.2 O(CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 OCH.sub.2 O).sub.n CH.sub.2 CH.sub.2 SH (III)
wherein n may vary from 0 to about 6 depending on the relative concentrations of II, NaHS and the H 2 S pressure. A higher concentration of NaHS and increased H 2 S pressure results in lower values of n. If desired III wherein n is 0 (IIIa) may be distilled from the originally prepared III which one skilled in the art will readily appreciate to contain a mixture of n values. Similarly fractions of III having greater n values may be obtained from the originally prepared mixture by standard separation techniques, for example, molecular sieve chromatography. IIIa may be treated with dibutyl tin oxide in an inert solvent, conveniently n-butanol or toluene, at moderately elevated temperatures, conveniently about 80° to 120° C., preferably about 110° to 115° C., until evolution of water formed during the reaction ceases. If desired, Ia so formed may be recovered from the reaction mixture by standard techniques.
It will be obvious to one skilled in the art that bis (ω-chloro-alkyl) formals and bis (ω-chloro-alkyl) ethers may also be reacted with sodium hydrosulfide and hydrogen sulfide in similar fashion to that illustrated hereinabove, that the products so formed may be separated into their relative molecular sizes or mixtures thereof by standard techniques as described hereinabove and that these products may be reacted with known dialkyl or diaryl tin oxides to produce the other compounds contemplated under Formula I. Similarly II may be reacted with other known dialkyl or diaryl tin oxides to produce still other compounds of Formula I.
The compounds of the invention also possess pesticidal activity and they may be employed in standard formulations well known in the art for that purpose. Ia, for example, may be employed at concentrations up to 3% as an antibarnacle additive in standard marine paint formulations.
The following examples further illustrate the best mode contemplated by the inventor for the practice of his invention.
EXAMPLE 1
Dimercaptoethyl Formal
Bis (β-chloroethyl)formal (173 g.) in water (1000 ml.) is stirred with NaHS (320 g.) under H 2 S (20 psi.) for 48 hours. At the end of this period, the layers are separated and the organic phase washed several times with water and dried to give a crude product (150 g.). Distillation gives the title product (BPt. 80° C., 0.5 mm. of Hg absolute pressure).
Analysis for C 5 H 12 O 2 S 2
Calc: S, 38.2%
Found: S, 37%
EXAMPLE 2
7,7,17,17-tetrabutyl -1,3,11,13-tetraoxa -6,8,16,18-tetrathia -7,17-Distannacycloeicosane
Bis (β-thioethyl) formal (100.3 g.) is stirred in toluene (150 g.) with dibutyltin oxide (114.2 g.) at about 85° to 115° C. while collecting the water evolved over a 40 minute period. At the end of this period water evolution ceased and refluxing is continued at about 115° C. for an additional 2 hours and the mixture cooled to room temperature. The solvent is removed in vacuo. The residue is taken up in methyl ethyl ketone and filtered through filter paper and the filtrate evaporated in vacuo to give the title product as an oil (180.2 g.)
Analysis for C 26 H 56 O 4 S 4 Sn 2 Found: C, 39.86; H, 7.54; S, 17.51; Sn, 0.36%
EXAMPLE 3
Formulations are prepared by hot mixing Geon 103 (100 parts by weight) and dioctyl phthalate (20 parts by weight) (A) and Geon 103 (100 parts by weight), dioctyl phthalate (20 parts by weight) and the product of example 2 (0.5 parts by weight) (B).
Initially A had a chocolate brown color and B had a very light yellow color. At the end of 1 day exposure to broad spectrum UV light A had a dark brown coloration tending to black while B maintained its light yellow color. At the end of 2 weeks, A had attained a jet black color while B was brown tinged black.
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Tin salts formed by the reaction between di-lower alkyl or diaryl tin oxides, and dimercaptoethyl formal and similar dimercapto compounds are disclosed. The final products are useful as ultraviolet light stabilizers for poly(vinyl chloride) resins and for the articles produced therefrom.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and benefit of an earlier filed co-pending Provisional Patent application Ser. No. 61/323,537 filed Apr. 13, 2010 entitled Engineered Steel Crib for Use as Mine and Tunnel Support.
FIELD OF INVENTION
[0002] This invention relates primarily to the mining, tunneling, and construction industries and, more specifically, to an engineered steel crib for the support of hanging wall and foot wall, roof and floor, or upper and lower surfaces in underground mining, or providing temporary support for heavy structures such as ships, cars, houses or buildings being relocated or receiving foundation work.
BACKGROUND OF INVENTION
[0003] Wooden posts and wooden cribs, or chocks, are probably the oldest support systems used in the mining and construction industries. A wooden post, typically 4 inches to 10 inches in diameter or square cross-section, loaded axially provides support between two points. A wooden crib or chock provides support over a larger area, typically varying from a 30 to 72 inches square or rectangle. Wooden posts and wooden cribs are extensively used in the mining industry even today.
[0004] A wood crib consists of layers of two or more parallel timbers with adjoining layers placed at right angles to each other. Thus, the number of parallel timbers in each direction determines the number of contact areas through which load is transferred or resisted. For example, a 2-by-2 crib means two layers of timber in each direction, resulting in 4 contact areas. A 2-by-2 crib configuration is most common, although 3-by-3, 3-by-2, 3-by-3, and 4-by-4 configurations have been considered and have found limited application.
[0005] Underground mines use large numbers of wooden cribs to provide support over an area between two opposing surfaces rather than at a point as with a wooden post. These opposing surfaces are referred to differently in different mining industries. For example, the lower surfaces in mines may be referred to as the floor or footwall, and the upper surfaces as the roof or hanging wall. Typically, cribs are more extensively used in longwall and high extraction room-and-pillar coal mining. Cribs are also extensively used in non-coal underground mining.
[0006] A crib is typically constructed of wooden elements of square or prismatic cross-section, 5 to 6 inches across, although other shapes have also been used. The length of elements used typically varies from 30 inches to 60 inches, depending upon the height of the area to be supported. The term ‘aspect ratio’, when used in conjunction with a crib, denotes the ratio of the height of the crib to the distance between centers of contact areas along a timber. Reducing aspect ratio increases the stability of the crib structure, and ratios larger than 2.5 and less than 4.3 are recommended. A crib structure should be designed to have appropriate rigidity, or stiffness, and load carrying capacity to provide early, controlled resistance to rock mass movement to maintain excavation stability.
[0007] A typical crib uses solid, prismatic wooden crib elements of 5″-by-5″-by-30″ or 6″-by-6″-by-36″, although other sizes may be used. The load is transferred between upper and lower surfaces through typically four contact areas in a horizontal plane of the size 5″-by-5″ or 6″-by-6″ depending on the size of the crib element. Except at and around the contact areas, there is very little stress or force within the prismatic element. The areas adjacent to the contact areas are in tension while zones away from contact areas have almost no stresses vertically or horizontally. At and below the contact areas are high compressive stresses due to load transfer.
[0008] Wood is a transversely isotropic material with much higher strength and stiffness when loaded axially, or parallel to the grain, as compared to loading transversely, or perpendicular to the grain. More specifically, a typical oak timber loaded axially has a compressive strength of 2000-2500 psi and an elastic modulus of 150,000-250,000 psi. Similar data for the two lateral loading directions are about equal to each other, and a typical oak timber has a compressive strength of 500-700 psi and an elastic modulus of 25,000-35,000 psi. Furthermore, the Poisson's ratios for loading in the axial and lateral directions are also significantly different: 0.10-0.20 for loading axially and 0.30-0.40 for loading in the two lateral directions. The type of wood and the engineering data included here are provided as an example and these may vary over a wide range.
[0009] A typical solid wood cribbing for support has several disadvantages, including: low rigidity, a limited load carrying capacity, a high resistance to airflow, heavy weight per crib element, limited pre-load capacity, insufficient post-failure characteristics, flammability, and shrinkage.
[0010] A typical wood crib's rigidity is low since wood is loaded at right angles to grain. So; the support column allows a significant amount of deformation, as much as 20% of the total height of the column may be reduced through deformation.
[0011] Because of large deformations, the column has limited load carrying capacity; a typical crib column fails due to buckling before achieving its full load carrying capacity.
[0012] Air flow in mines is important. Since each crib column reduces the available air flow space when installed, resistance to air flow can be significant.
[0013] Installing typical solid wood crib element is difficult in locations where the surfaces are not parallel to each other or irregular.
[0014] Each wooden crib element typically weighs about 35 pounds, making carrying them by hand and assembling a crib column an arduous process, especially when one must lift an element above one's head.
[0015] Since low-rigidity wedges, cut parallel to the wood grain, are typically used to preload the crib, the amount of preload force that can be introduced to a column is limited and it tends to decay with time. The wedges typically deform under low loads, which means that the column does not support significant loads until the upper and lower surfaces have deformed toward each other, through compression of the column. Preloading is currently applied through wooden wedges, typically 3 to 4 inches wide that are cut at inclination angles of 10 to 20 degrees. These wedges are loaded transversally to the wood grain and yield at the low pressure of 500 to 700 psi. For wedges cut at high inclination angles, the contact areas with prismatic crib elements are small. Therefore, stress concentrations at contact points are high and the wedges yield even at low crib loads. The wedges then become loose providing little or no preload on the installed crib. Industry professionals suggest that there is a need to develop a relatively simple mechanism to apply a sustained preload of 5 to 8 tons when a crib is installed. Moreover, wood shrinks as it loses moisture. Upon shrinking it loses the preinstalled load and industry is seeking ways to minimize this problem.
[0016] In addition to the above, the post-failure characteristics of wood do not provide a relatively flat load-deformation curve and wood is flammable.
[0017] The use of steel or other similar material for mine support and tunnel cribbing would solve most of the problems inherent in the wood cribbing. Steel is more rigid than wood, and, when used in a support column, has a greater load carrying capacity without the risk of buckling failures present in wood cribbing. A steel crib support column can support a sustained preload when it is installed and does not lose this preinstalled load through shrinking, as is common in wood cribbing. Additionally, steel provides a relatively flat post-failure load-deformation curve and steel is not flammable. However, despite the advantages of using steel, it has only found limited use as a material in cribbing elements because solid steel is heavy and expensive. Understandably, steel would not be a suitable material to construct prior art cribbing elements; a conventional solid cribbing element made of steel would be very heavy. Steel has been extensively used in steel supports such as arches, and bars (U.S. Pat. Nos. 3,991,580; 3,952,525; 7,909,542; 5,484,130), and either as reinforcement for concrete (U.S. Pat. No. 4,497,597) or as only a part of the load carrying element in wood (WO 00/53892) and cement-concrete (U.S. Pat. No. 4,565,469) crib elements.
[0018] The present invention utilizes an innovative design to construct a light-weight steel crib element with all of the desired characteristics for a crib element as well as low resistance to airflow. Furthermore, the innovative design should find applications beyond mining and tunneling industries such as in construction, railroad and ship building industries.
SUMMARY OF THE INVENTION
[0019] This invention provides an improved cribbing support in mines and tunnels through a lightweight, engineered steel crib element to provide support between two surfaces. It is easy to carry manually and offers very low resistance to airflow depending upon the selected embodiment. The elements can be used in multiple ways to construct cribs. The element provides high stiffness support to develop a crib with literally any desired load carrying capacity. However, it is anticipated that initially cribbing with load carrying capacity of 100-tons to 300-tons will be commonly used to minimize rock mass movement in mines and tunnels.
[0020] The steel crib element consists of one or more center elongate structural elements, connected at the distal ends of the elongate structural element to at least two outer hollow or solid steel load carrying members. The hollow or solid steel load carrying members may be perforated with holes, and loaded axially or parallel to its longitudinal axis, or laterally or perpendicular to its longitudinal axis depending upon a selected embodiment among the many in each configuration. The hollow load carrying members may be internally reinforced or filled with appropriate materials to achieve desired load-deformation characteristics. The elongate structural elements may be prismatic or round or any other shape in cross-section and may use steel or any other suitable material (metal, non-metal, polymer composites, etc) that have appropriate load carrying capacity, load-deformation characteristics, and material cost. The connection between elongate structural elements at the distal ends and load carrying members may be through nuts and bolts, welds, screws, or other suitable fastening means or polymeric materials. The elongate structural elements, connecting the load carrying members, may also be interconnected among themselves at suitable intervals to provide required flexural rigidity and load carrying capacity in different spatial planes. The crib structure is constructed similar to wooden cribbing by superimposing only these crib support elements in 2×2 layers, 2×3 layers, 3×3 layers, or other suitable layered system. To ensure full contact area between load carrying members of different elements and to minimize likelihood of slippage or limit lateral movement between mating surfaces of different elements, the crib element design includes indexing as well as interlocking stops. The upper and lower plates installed on the hollow load carrying steel tubes may be flat with skid resistant material on the top, “diamond plate” design with curved raised surfaces to allow interlocking and minimize lateral movement or slippage, embossed with suitable design, or may have short pins that fit into holes in the mating plates depending upon the embodiment selected.
[0021] The novel crib element offers the following advantages: it has much higher stiffness (10-20 times or more) than the wooden cribs (about 40,000 psi) commonly used today; it can be designed to have variable stiffness; it can be designed to support any loads but typically varying from 100 tons to 300 tons for a 6-ft high cribs; it has the ability to sustain almost peak load even after the steel starts to yield; it is lightweight; it may offer very low resistance to airflow in underground mine roadways; and, it does not shrink like the wooden cribs that are almost exclusively used today in mining and tunneling industries.
BRIEF DESCRIPTION OF THE DRAWING
[0022] FIG. 1 —( a ) A side view of a steel crib element with a solid load carrying member and a flat plate or bar elongate structural element; ( b ) A top view of the steel crib element.
[0023] FIG. 1 A—(a) A sectional view of a steel crib element with hollow load carrying members and a flat plate or bar elongate structural element; (b) Another sectional view of the steel crib element.
[0024] FIG. 1 B—(a) A top view of a steel crib element with hollow load carrying members with recessed grooves for mating adjoining steel crib elements and a flat plate or bar elongate structural element; (b) A sectional view of the steel crib element.
[0025] FIG. 1 C—(a) A top view of a steel crib element with hollow octagonal load carrying members and a flat plate or bar elongate structural element; (b) A sectional view of the steel crib element. This figure may need revision.
[0026] FIG. 1 D—(a) A side view of a steel crib element with hollow perforated load carrying members and a flat plate or bar elongate structural element; (b) A top view of the steel crib element.
[0027] FIG. 1 E—(a) A sectional view of a steel crib element with hollow load carrying members with indexing and mating top and bottom caps and a flat plate or bar elongate structural element; (b) A top view of the steel crib element.
[0028] FIG. 1 F—(a) A top view of a steel crib element with hollow cylindrical load carrying members and two interconnected elongate structural elements; (b) A sectional view of the steel crib element.
[0029] FIG. 1 G—(a) A top view of a steel crib element with three hollow load carrying members and interconnected elongate structural elements; (b) A side view of the steel crib element.
[0030] FIG. 1 H—(a) A top view of a steel crib element with hollow load carrying members and two interconnected elongate structural elements; (b) A side view of the steel crib element.
[0031] FIG. 2 —( a ) A sectional view of a steel crib element with hollow load carrying members reinforced internally with steel plate and two interconnected elongate structural elements; ( b ) Another sectional view of the steel crib element.
[0032] FIG. 3 —( a ) A top view of a steel crib element with hollow load carrying members with cylindrical mating and indexing elements and two interconnected elongate structural elements; ( b ) A sectional view of the steel crib element.
[0033] FIG. 4 —( a ) A top view of a steel crib element with hollow load carrying members with diamond pattern cap plates and two interconnected elongate structural elements; ( b ) A side view of the steel crib element.
[0034] FIG. 5 —( a ) A sectional view of a steel crib element with hollow steel load carrying members with wood reinforcements and two interconnected structural elements; ( b ) Another sectional view of the steel crib element.
[0035] FIG. 6 —A perspective view of the crib elements stacked into a 2×2 crib structure.
[0036] FIG. 7 —A planar view of stacked crib elements forming a crib support between the mine floor and roof.
[0037] FIG. 8 —A planar view of stacked crib elements forming a crib support between the mine hanging wall and footwall.
[0000]
Reference Numerals in Drawings
Reference Numerals in Drawings
1
Steel Crib Element
5
Mine Floor
6
Mine Roof
7
Hanging Wall
8
Footwall
9
Wedges
10
Elongate Structural Element
21
Hollow Load Carrying Member
22
Solid Steel Load Carrying Member
27
Round or Prismatic Bar Elongate Structural Elements
28
Triple Reinforcing Bar Elongate Structural Elements
36
Interconnections Between Elongate Structural Elements
25
Raised Lateral Movement-Resistant Material (Diamond Plate)
23
Cylindrical Indexing and Mating Element
26
Flat Bar Elongate Structural Elements
31
Fastening Means
32
Flat Bar Internal Reinforcements
40
Sides of Load Carrying Member
42
Load Carrying Outer Surface
44
Indexing Protrusion
46
Indexing Grooves
47
Octagonal Top of Load Carrying Member
48
Sides of Octagonal Load Carrying Member
52
Perforated Structural Element
54
Top or Bottom Cap with Mating Protrusions
55
Bottom or Top Cap with Mating Grooves
56
Cylindrical Load Carrying Member
62
Hollow
64
Wood or Other Material Reinforcements
DETAILED DESCRIPTION
[0038] A conceived steel crib may consist of two or more pieces of metal load carrying members of any geometrical cross-section connected to each other through one or more elongate structural elements. The elongate structural elements may be rod of any shape or plate metal or any other material that provides appropriate load-deformation characteristics prior to and after yielding, has appropriate flexural rigidity in different orientations, and is reasonable in cost. The material used may also have any geometry that satisfies the above requirements. Mechanistically, the size of the load carrying member, its wall thickness, its geometry (square, rectangle, circular), and its loading orientation control its stiffness and load-deformation characteristics. The elongate structural elements may be metal rod or bar, non-metal, or polymers. The elongate structural elements may be interconnected at suitable intervals to provide appropriate strength and stiffness in different spatial planes. Similarly, the internal hollow portion of the hollow load carrying members may be reinforced with any material such as: metal, wood, plastic, and cementitous or pozzolonic material in various geometric configurations to achieve desired strength and to further modify the load-deformation characteristics of the crib element. The type and spatial distribution of lateral connections between the tubes (round, prismatic, solid, hollow) and the type of reinforcements (square, round, prismatic) between the lateral connections allow the ability of the crib to carry differential loading in different planes and twisting of the cribbing structure. The crib element is loaded so that it is either loaded transversely or loaded axially with respect the axis of the load carrying members.
[0039] In the embodiments where the hollow tube load carrying member is loaded axially, the upper and/or lower surfaces of the load carrying member may be covered with a lateral-movement resistant designs including but not limited to the following: solid or perforated steel plate; steel plate with roughened surfaces, such as “diamond plate” material available commercially; suitably embossed plates of any material, any thickness, and any shape; or protruded surfaces on one end with appropriate mating surfaces on the other end.
[0040] Additionally, the design of the hollow load carrying member may be shaped to provide interlocking between stacked crib elements.
[0041] To date, all experimental studies have been performed on Grade B or Grade C steel 30-inch long crib elements with load carrying members constructed of ASTM A-500 steel tube of 3/16-inch wall thickness. Grade B steel has a minimum yield stress of 46,000 psi and minimum tensile strength of 58,000 psi, while Grade C has a minimum yield stress of 50,000 psi and minimum tensile strength of 62,000 psi. The elongate structural elements also have similar strength and elastic properties. Steel tubes with up to 100,000 psi yield stress are available in a variety of wall thicknesses. Several of these may provide feasible desired crib element but the weight of the element and cost of the element could be very different.
[0042] The design of the structure above allows it to be lightweight, with the ability to withstand large amount of deformations because of the characteristics of steel or other materials used and reinforcements within the hollow load carrying members. The weight of each crib element will vary based on load carrying capacity. For a single element with ability to carry about 120-tons of load for a 2×2 crib, the weight of the designed element is only 20-21 pounds. Since most cribs used in mining and tunneling applications are designed to carry loads varying from 100-tons to 200-tons with four loading surfaces, all embodiments tested are suitable for use in mine and tunnels. The design of the cribs may be varied to meet the load carrying requirements of different structural applications.
[0043] The length of the load carrying members and elongate structural elements can be varied to achieve desired aspect ratio (height to width ratio). All studies to date have been performed on 30-inch or 36-inch long steel cribs with two load carrying steel members per crib. Longer cribs such as 42-inch, 48-inch, 54-inch, or 72-inch cribs can easily be developed based on this disclosure by adjusting the dimensions of the load carrying members and elongate structural elements and/or by connecting three or four load carrying members in series. Crib elements with three or four load carrying members may be configured at equi-distances along the length of the crib element (a preferred embodiment) or staggered.
[0044] The overall cribbing structure is constructed similarly to conventional wooden cribbing structure and that is by stacking crib elements. The cribbing structure is tightened between the roof and floor or hanging wall and footwall through steel inserts, wedges, grout bags, wooden wedges or other suitable materials which have high rigidity and will not shrink. Thus, a high preload can be applied to the crib during its construction process. Preferably, the material used for the wedges has a similar stiffness to the load carrying member to apply a maximum preload to the constructed steel crib structure. In preferred embodiments, the wedges are constructed of steel and are 3-inches wide to 5-inches wide to keep their weight to a minimum. Other sizes and materials for tightening the crib are within the scope of this invention. The steel wedges or inserts can also be manufactured from hollow steel tube.
[0045] The embodiments of the present invention are best described in reference to the figures. The crib element embodied in FIG. 1 is constructed of two 6-inch×6-inch×6-inch pieces of solid steel as the load carrying structural members 22 ; these load carrying structural members 22 are connected through an elongate structural element 10 composed of A36 steel flat bar 26 , 6-inch wide and ⅛-inch thickness. Other gauges of steel or other materials may be used. This elongate structural element 10 is attached at the distal ends to the load carrying member 22 via fastening means 31 such as welds or bolts. Alternately, other metals with other dimensions may be used as the load carrying member 22 for specific applications. Furthermore, the load carrying member 22 does not have to be square in cross-section. The elongate structural element 10 in this embodiment may also be composed of flat bar or plate sizes varying from 3-inch to 10-inch wide or more, with thicknesses ranging from ⅛-inch to ½-inch. The crib element is loaded perpendicular to the axis of the load-carrying structural member 22 . The load carrying capacity of this embodiment is about 80-tons.
[0046] The crib element embodied in FIG. 1A is constructed of two 6-inch×6-inch steel tubes with 3/16-inch wall thickness as the load-carrying structural members 21 ; these hollow load-carrying structural members 21 are connected through an elongate structural element 10 composed of A36 steel flat bar 26 , 6-inch wide and ⅛-inch thickness attached to the load carrying member 21 at the distal ends via fastening means 31 such as welds or bolts. Alternatively, other gauges of steel may be used and other metals may be used for both the elongate structural element 10 and the load carrying member; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying member 21 . Furthermore, the tubes do not have to be square in cross-section. The elongate structural element 10 in this embodiment may also be composed of flat bar or plate sizes varying from 3-inch to 10-inch wide, with thicknesses ranging from ⅛-inch to ½-inch or more. The crib element is loaded perpendicular to the axis of the hollow load carrying structural member 21 . The load carrying capacity of this embodiment is about 80-tons.
[0047] Alternately, to ensure full contact area between load carrying members of different elements and to minimize lateral movement between mating surfaces of different elements, the crib element design may include different designs for indexing or mating elements as well as limiting displacements under load between the mating elements. The upper and lower plates installed on the hollow load carrying steel tubes may also be embossed, may have short pins that fit into holes in the mating plates, or have curved raised surfaces to provide interlocking and indexing. In the embodiment represented in FIG. 1B , the load carrying member has the addition of indexing grooves 46 and protrusions 44 to enable mating between crib elements to impart structural stability in the constructed cribbing structure. The load bearing element 21 in this embodiment can be open at the top and/or bottom.
[0048] Indeed, mating of upper and lower surfaces of elements in a crib structure can be accomplished through a variety of methods, such as in the embodiment represented in FIG. 1E , with the addition of top and/or bottom caps with mating protrusions 55 and grooves 56 . The mating protrusions and grooves can be of any shape and size as long as they are complementary. Indeed, complementary mating protrusions and grooves can also be embossed into the metal load-carrying member or can be accomplished through complementary perforations 52 in the load carrying member as represented in FIG. 1D . The implementation of perforations 52 in the load-carrying structural member 21 also imparts another advantage in that the weight of the overall crib element is reduced for applications where crib weight is critical.
[0049] In the embodiment represented in FIG. 1C , the load carrying member 47 is octagonal in cross section. In this embodiment, the octagonal load carrying member 47 is hollow and has sides 48 . The embodiment represented in FIG. 1F has a hollow cylindrical load carrying structural member 56 . Indeed, the load carrying members can be some shape other than circular, octagonal, or square in cross-section. The load carrying member can be any shape in cross-section, including hexagonal, triangular, or polygonal.
[0050] In another embodiment of the present invention, represented in FIG. 1G , three load carrying members 21 are connected in series. These load carrying members 21 are connected through elongate structural elements 10 comprising two round bar elongate structural elements 27 with flat bar interconnections 36 between them in a truss configuration; this configuration better disseminates normal and shear stresses within the structure but other configurations and materials can be used depending on the application. More than three load carrying structural members can be connected in series at equi-distances or in staggered configurations for desired applications.
[0051] The crib element embodied in FIG. 1H is constructed of two 6-inch×6-inch steel tubes with 3/16-inch wall thickness as the load-carrying structural members 21 ; these hollow load-carrying structural members 21 are connected through an elongate structural element 10 composed comprising two round bar elongate structural elements 27 of ⅝-inch diameter A36 steel round bar with three steel flat bar interconnections 36 between them. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying member 21 . In this embodiment the opposing sidewalls are missing creating an open-ended cavity 62 .
[0052] In another embodiment of the present invention, represented in FIG. 2 , the load carrying member 21 is constructed with 6-inch×6-inch steel tube with 3/16-inch wall thickness with reinforcements 32 within each tube comprising two ⅛-inch×6-inch A36 steel plates in an X-configuration. Alternatively, the reinforcements 32 within the load carrying member 21 can be steel or metal of any configuration and gauge such as cylinders, bars, and triangles. These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 of ⅝-inch diameter A36 steel round bar with three ¼-inch×¾-inch steel flat bar interconnections 36 between them. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying member 21 . The load carrying capacity for this embodiment is about 140-tons.
[0053] Yet another embodiment of the present invention, constructed similarly to the crib element of FIG. 2 , the load carrying member 21 is constructed with 6-inch×6-inch steel tube with 3/16-inch wall thickness with reinforcements 22 within each hollow tube load carrying member 21 comprising two 1-inch×6-inch A36 steel plates (one vertical and one horizontal.) These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 of ⅝-inch diameter A36 steel round bars with one steel flat bar interconnection 36 between them. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , the reinforcements 22 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying members 21 . The load carrying capacity for this embodiment is about 120-tons.
[0054] In yet another embodiment of the present invention, constructed similarly to the crib element of FIG. 2 , the load carrying member 21 is constructed with 6-inch×6-inch steel tube with 3/16-inch wall thickness with cylindrical reinforcements within each tube comprising 1/16-inch thick steel tube. The cylindrical reinforcements 23 within each load carrying member 21 can be of similar height to the structural member or slightly smaller to be contained completely within the load carrying member 21 . These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 with three ¾-inch×¾-inch steel flat bar interconnections 36 between them. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , the reinforcements 22 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying members 21 .
[0055] In a similar embodiment, the load carrying member 21 is constructed with 6-inch×6-inch steel tube with 3/16-inch wall thickness with a cylindrical reinforcements within each tube. These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 with interconnections 36 between them. This crib element is loaded axially and the load carrying members 21 are constructed so that the hollow tube load carrying member 21 of one element rests at right angles to the hollow tube load carrying member 21 of the upper or lower element. In this configuration, each steel tube load carrying member 21 is allowed to yield and punch into the lower or upper tube. The two punched tubes interlock and provide load carrying and buckling strength to the crib. This embodiment of the present invention with a 6-inch square hollow steel tube load carrying member 21 and a 6-inch high cylindrical reinforcement 23 carried about 160-tons. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , the reinforcements 22 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying members 21 . This design can be modified for different load carrying capacity and stiffness.
[0056] In another embodiment of the present invention, represented in FIG. 3 , the load carrying member 21 has a cylindrical mating and indexing element 23 running substantially through the load carrying member 21 . In this embodiment, the cylindrical mating and indexing elements 23 are of similar height to the load carrying member 21 and slightly protrude through the top (providing a recess in the bottom of the element) to provide indexing and mating of upper and lower crib elements. This configuration also provides reinforcement to the load carrying member 21 . Alternatively, cylindrical mating and indexing element 23 may be composed of two separate elements: one a protrusion extending from the top of the load carrying member and the other a recess in the bottom of the load carrying member. Additionally, the cylindrical mating and indexing elements 23 need not be cylindrical and can be almost any shape in cross section including square or octagonal.
[0057] Yet another embodiment of the present invention, represented in FIG. 4 , the load carrying member 21 is constructed with 6-inch×6-inch hollow steel tube with 3/16-inch wall. These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 with three ¼-inch×¾-inch steel flat bar interconnections 36 between them. This crib element is loaded perpendicular to the axis of the load carrying member 21 and has ¼-inch×6-inch×6-inch raised-floor steel plates 25 attached to the top and bottom of the load carrying members 21 via fastening means. The use of the diamond-pattern raised floor steel plates 25 allowed only about 0.25-inch of lateral displacement between the two mating steel cribs while carrying over 200-tons (limited by the capacity of the testing machine.) Again, alternatively, other gauges, configurations, and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the diamond-pattern raised floor plates 25 , the interconnections 36 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying members 21 .
[0058] In another embodiment of the present invention, represented in FIG. 5 , the hollow load carrying member 21 is reinforced with a prismatic wooden element 64 . These load carrying members 21 are connected through an elongate structural element 10 comprising two round bar elongate structural elements 27 of ⅝-inch diameter A36 steel round bar with three ¼-inch×¾-inch steel flat bar interconnections 36 between them. The crib element was loaded axially. This significantly increased the load carrying capacity and improved the post-failure load-deformation properties. The above characteristics can also be achieved by reinforcement of the hollow load carrying member 21 with a cementitious or pozzolonic material, polymeric material, metallic or non-metallic material, or any other suitable material. With such reinforcements, the load carrying member may be loaded axially or transversely. Alternatively, other gauges and sizes of steel may be used and other metals may be used for the elongate structural element 10 , the interconnections 36 , and the load carrying members 21 ; and other tubing sizes (3-inch to 10-inch or more), with different wall thicknesses (0.125 inch to 0.5-inch) could be used as the load carrying members 21 .
[0059] Yet another embodiment of the present invention, where the crib elements 1 are stacked in a 2×2 crib structure, is represented in FIG. 6 . The crib structure is constructed of crib elements comprising two 6-inch×6-inch steel tubes with 3/16-inch wall thickness as the load carrying members 21 ; these hollow load carrying members 21 are connected through an elongate structural element 10 comprising three (3), ½-inch diameter steel concrete reinforcing rods 28 , without any interconnection between the rods. The elongate structural element runs along the entire length of the crib element 1 , and is attached to the far interior of the hollow load carrying member 21 via fastening means 31 such as welds or bolts; this configuration allows the elongate structural element 10 to also provide reinforcement to the load carrying member. These crib elements 1 are loaded transversely.
[0060] Yet another embodiment of the present invention, where the crib elements 1 are stacked in a 2×2 crib structure between the floor 5 and roof 6 of a mining excavation, is represented in FIG. 7 . The first and second lower crib elements 1 are spaced apart substantially parallel to each other and placed on the floor 5 . The upper first and second crib elements 1 are then placed on top of the lower first and second crib elements 1 . These first and second upper crib elements 1 are aligned parallel to each other and placed orthogonally with respect to the orientation of the lower first and second crib elements 1 . These crib elements 1 are stacked in such a manner between the roof 6 and floor 5 of a mine and a preload is applied through the use of suitable material wedges 9 .
[0061] Another embodiment of the present invention, where the crib elements 1 are stacked in a 2×2 crib structure between the hanging wall 7 and footwall 8 of a mining excavation, is represented in FIG. 8 . The first and second lower crib elements 1 are spaced apart substantially parallel to each other and placed on the footwall 8 . The upper first and second crib elements 1 are then placed on top of the lower first and second crib elements 1 . These first and second upper crib elements 1 are aligned parallel to each other and placed orthogonally with respect to the orientation of the lower first and second crib elements 1 . These crib elements 1 are stacked in such a manner between the hanging wall 7 and footwall 8 of a mine and a preload is applied through the use of suitable material wedges 9 .
[0062] Although the above discussion relates to steel construction, the principles apply equally to construction of similar designs using other materials. The sizes of the load carrying members, elongate structural elements, and reinforcements indicated throughout the application are only suggestions and not meant to be limiting. The developed concepts can also be utilized in the design of tunnel arches.
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This invention provides improvements through an engineered metal crib element for construction of cribs in mines to provide support between two surfaces and use of crib elements to construct cribs. The engineered metal crib element consists of a center elongate structural element and at least two outer load carrying steel members. The outer load carrying members may be composed of solid or hollow metal with one or more reinforcements within each load carrying member. Each outer load carrying member is attached to the center elongate element at the distal ends of the elongate structural element. The crib structure may be constructed by superimposing only these steel crib elements in 2×2 layers, 2×3 layers, 3×3 layers or in any other suitable layering system. The engineered metal crib elements are lightweight, have controllable higher stiffness and load carrying capacity than current wooden cribs, have engineered plastic yielding characteristics and allow much lower resistance to air flow in underground mine roadways.
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This is a division of application Ser. No. 663,638, filed Oct. 22, 1984.
BACKGROUND OF THE INVENTION
The present invention relates in general to an electric brake controller for energizing electrically operated brakes in a towed vehicle and, in particular, to an electric brake controller which incorporates a means for sensing the deceleration of the towing vehicle and for generating a brake energizing signal as a function of the deceleration.
Recreational and utility trailers adapted to be towed by automobiles and small trucks and many similar towed vehicles are commonly provided with electric brakes. The electric brakes generally comprise a pair of brake shoes which, when actuated, frictionally engage a brake drum. An electromagnet is mounted on one end of a lever coupled to actuate the brake shoes. When an electric current is applied to the electromagnet, the electromagnet is drawn against the rotating brake drum which pivots the lever to actuate the brakes. Typically, the braking force produced by the brake shoes is proportional to the electric current applied to the electromagnet.
To ensure proper operation, a control system for electrically operated brakes must be easily adjustable to accommodate different relative weights of the towed and towing vehicles. Also, the control system must be predictable to give the driver of the towing vehicle a feeling of smooth and positive brake operation both upon applying and releasing the brakes in the towing vehicle.
In one type of electronic brake control system, such as the system disclosed in U.S. Pat. No. 4,295,687, the electric brakes are actuated in response to the operation of the towing vehicle's brake pedal by the driver. In this system, a transducer produces a brake control signal corresponding to the desired braking effort by sensing either (1) the hydraulic pressure in the braking system of the towing vehicle or (2) the pressure applied by a driver's foot to the towing vehicle's brake pedal. A pulse width modulator is responsive to the brake control signal for generating a fixed frequency pulsed output signal having a duty cycle proportional to the amount of braking effort desired.
Various towed vehicle braking systems have been proposed wherein the braking of the trailer is automatically controlled by the sensing of deceleration forces. For example, U.S. Pat. Nos. 2,242,153; 2,642,961; 2,779,443; 2,856,036; and 2,969,857 all disclose automatic brake applying systems wherein the deceleration inertial force imposed upon the hitch by the trailer during deceleration of a towing vehicle is sensed and used to effect braking of the trailer.
Also, it has been proposed to use a pendulum or a mass movement sensing device for sensing the deceleration of a towing vehicle and for operating either a mechanical or an electrical braking system in the towed vehicle. Examples of such pendulum systems are disclosed in U.S. Pat. Nos. 2,870,876 and 3,053,348.
One type of electronic brake controller which includes a pendulum unit for sensing the deceleration of the towing vehicle is disclosed in U.S. Pat. No. 3,953,084. In this patent, the pendulum is provided with a shield to block the passage of light from a light source to a light sensing unit when the pendulum is in a resting position. When the brakes of the towing vehicle are operated and the vehicle decelerates, the pendulum will swing to permit light to fall on the light sensing unit which then generates a control signal. The brake controller is responsive to the control signal for producing a pulsed output signal having a fixed frequency and a variable pulse width proportional to the level of the control signal.
SUMMARY OF THE INVENTION
The present invention relates to a self-contained electric brake controller which incorporates a unique deceleration sensing unit for generating a signal proportional to the magnitude of deceleration of the towing vehicle. The controller includes a circuit responsive to the deceleration signal for generating a brake driving signal to control the brakes of the towed vehicle.
The deceleration sensing unit of the present invention includes a support means such as an outer housing adapted to be secured relative to the towing vehicle and a pendulum mounted on an axis for pivotal movement relative to the housing. The pendulum is movable in one direction from a resting position to a predetermined extended position when the vehicle is subjected to a predetermined amount of deceleration. Means are coupled to the pendulum for generating a signal corresponding to the predetermined extended position of the pendulum. This signal represents the predetermined amount of deceleration to which the vehicle is subjected.
In accordance with the present invention, the deceleration sensing unit includes means for applying a restoring force to the pendulum to resist further movement of the pendulum in the one direction from the extended position. It has been found that by providing such a restoring force, the outward movement of the pendulum is limited and the pendulum can be returned to its resting position more rapidly than if gravity provided the sole restoring force. This stabilizes the operation of the controller and provides more accurate braking control. In the preferred embodiment of the invention, the pendulum includes a first magnet spaced from the pivot axis of the pendulum, and the restoring force is produced by a second magnet carried by the housing and spaced from the pendulum. This second magnet is adapted to produce a magnetic field which, as the pendulum swings to its extended position, opposes the magnetic field produced by the first magnet and exerts a magnetic force on the pendulum to retard further movement of the pendulum in the one direction.
Also, the deceleration sensing unit includes damping means which is spaced from the magnet carried by the pendulum for reducing undesirable movement of the pendulum. The damping means is typically constructed of a ferromagnetic material which is attracted to the pendulum magnet in a direction perpendicular to the movement of the pendulum. The ferromagnetic material dampens the movement of the pendulum such that sudden forces transmitted to the pendulum such as road shocks, for example, will not cause undesirable movement of the pendulum.
In the preferred embodiment of the invention, the means coupled to the pendulum for generating a signal corresponding to the predetermined extended position of the pendulum includes a detector such as a Hall effect device which is carried by the housing and is spaced from the magnet of the pendulum. The detector is responsive to the magnetic field generated by the magnet for generating a position signal representing the predetermined extended position of the pendulum. This position signal corresponds to the predetermined magnitude of deceleration of the vehicle.
The control circuit which is responsive to the deceleration signal generated by the deceleration sensing unit includes several unique features. Typically, the control circuit includes a control means responsive to an activation signal and the deceleration signal for generating a brake control signal representing a predetermined amount of braking. A comparator means compares the voltage level of the brake control signal with the voltage level of a sawtooth waveform to produce a pulse width modulated signal having a duty cycle corresponding to the predetermined amount of braking. This pulse width modulated signal is supplied to an output drive means for generating a brake driving signal to energize the brakes.
In the circuit of the present invention, the activation signal is generated when the driver either (1) steps on the vehicle brake pedal to close a stop light switch or (2) actuates a manual control switch, either of which supplies the activation signal at the voltage level of the vehicle power source. The circuit is provided with means responsive to the activation signal for disabling the output drive means when the voltage level of the activation signal is below a predetermined level. This prevents the electric brake controller from generating a brake driving output signal in instances wherein, due to circuit problems such as an insufficient ground in the stop light circuit, the control means receives a lower level activation signal when neither the stop light switch or the manual control has been actuated.
Also, the present invention includes means for sensing the current load on the brake driving signal to protect the output drive means in the event of a full or partial short circuit condition. Such sensing means are responsive to a sensed current load progressively exceeding a predetermined level for progressively increasing the average voltage level of the sawtooth waveform, thus causing the comparator means to reduce the duty cycle of the pulse width modulated signal. Thus, in the event of a partial short circuit condition, limited braking is maintained.
In the present invention, a foot actuated means such as a brake pedal stop light switch can be utilized to generate a first brake control signal representing a first desired amount of braking, while a hand actuated means such as a manual control can be used to generate a second brake control signal representing a second desired amount of braking. With the present invention, means are responsive to the first and second brake control signals for generating a composite brake control signal representing the combined braking of the first and second braking control signals.
BRIEF DESCRIPTION OF THE DRAWINGS
The above, as well as other advantages of the present invention, will become readily apparent to one skilled in the art from reading the following detailed description in conjunction with the attached drawings, in which:
FIG. 1 is a schematic diagram illustrating an electric braking system utilizing an electric brake controller according to the present invention;
FIG. 2 is an enlarged perspective view illustrating a deceleration sensing unit incorporated in the brake controller of FIG. 1;
FIG. 3 is a sectional view of the deceleration sensing unit taken along the line 3--3 of FIG. 2;
FIG. 4 is a side sectional view of the deceleration sensing unit taken along the line 4--4 of FIG. 3;
FIG. 5 is a block diagram illustrating the electronic control circuit of the present invention;
FIGS. 6a, 6b, and 6c are waveform diagrams illustrating signals generated by the circuit of FIG. 5; and
FIG. 7 is a schematic diagram illustrating a preferred embodiment of the circuit shown in FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, and particularly to FIG. 1, there is shown a schematic diagram of an electric brake system 10 which utilizes an electronic brake controller 12 embodying the principles of the present invention. The brake controller 12 is generally located in the towing vehicle and, when activated, functions to generate an electric signal on a line 14 to energize electric brakes 16 and 17 utilized to brake the wheels of the towed vehicle. The electric brakes 16 and 17 each include a pair of brake shoes 18 and 19 which, when actuated by a lever 20, are expanded into contact with a brake drum 21 for braking the wheels of the towed vehicle. A separate electromagnet 22 is mounted on an end of each of the brake actuating levers 20. Each electromagnet 22 is positioned to abut the generally flat side of a brake drum 21. As an electric current is passed through each of the electromagnets 22, the electromagnets are drawn into contact with the brake drums 21 and the resulting drag pivots the levers 20 to engage the brakes 16 and 17 in a conventional manner.
The towing vehicle typically includes a conventional hydraulic brake system 24 which is activated when a brake pedal 25 is depressed by the driver. The brake pedal 25 is coupled to a stop light switch 26 such that, when the brake pedal 25 is depressed, the switch 26 is closed and power from a vehicle power supply 27 is applied to one or more brake lights 28. The vehicle power supply 27 is also connected to provide power to the controller 12 on a line 27a. When the stop light switch 26 is closed, power is supplied on a line 29 as an activation signal to activate the controller 12.
When the stop light switch 26 is closed and the controller 12 is activated, the controller 12 functions to generate an electric output signal on the line 14 having a current which is directly proportional to the braking force applied to the towing vehicle. In order to generate such a signal, the controller 12 incorporates a unique means for sensing the deceleration of the towing vehicle and for generating a signal which is a function of the deceleration of the vehicle. Such a deceleration sensing unit is generally indicated in FIG. 1 by reference numeral 30. As shown in FIG. 1, the deceleration sensing unit 30 is located within an outer casing 31 of the electronic controller 12. As will be discussed in more detail hereinafter, the deceleration sensing unit 30 includes a pendulum adapted to swing in one direction when the towing vehicle is decelerating, and means for generating a signal representing the amount of swinging movement of the pendulum. Also, the deceleration sensing unit includes a leveling means 33 which, as will be discussed, extends from the side wall of the casing 31 and is utilized to level the sensing unit 30 after the casing 31 has been securely mounted to the vehicle.
In some instances, it may be desirable to only actuate the brakes 16 and 17 in the towed vehicle. This may be desirable, for example, to stabilize the towed vehicle against vacillations or swinging caused by strong side winds. Therefore, a manual slide control 34 is provided on the electronic controller 12 to allow the vehicle driver to manually apply the towed vehicle brakes 16 and 17 without applying the towing vehicle brakes.
The electronic controller 12 also is provided with a manual gain control 36. The gain control 36 allows the vehicle driver to compensate for different loads in the towed vehicle. For example, as the load in the towed vehicle increases, it is necessary to increase the braking force in the towed vehicle relative to the braking force applied in the towing vehicle. By adjusting the gain control 36, the power applied by the electronic controller 12 to the electromagnets 22 may be increased or decreased for any given output from the deceleration sensing unit 30.
The electronic brake controller 12 includes an indicator light 38. The intensity of the light 38 is proportional to the average current level of the signal generated on the line 14 used to actuate the towed vehicle brakes 16 and 17. The light 38 provides a visual indication to the driver to show that the controller 12 is operating properly.
Referring to FIGS. 2 through 4, there are shown enlarged drawings illustrating a preferred embodiment of the deceleration sensing unit 30 of the present invention. The deceleration sensing unit 30 comprises an outer plastic housing 42 which is secured to a circuit board 43 supported within the controller casing 31. A pendulum 44 is supported for swinging movement relative to the housing 42 by means of a pivot pin 46. As shown in FIG. 3, the pivot pin 46 extends through apertures 42a and 42b formed in the side walls of the housing 42 and through spaced-apart low friction bearing elements 44a and 44b provided in the upper end of the pendulum. If desired, a lubricant can be introduced between the bearing elements 44a and 44b and the pin 46. The one end of the pin 46 is provided with a head portion 46a received by the leveling means 33, while the opposite end 46b is secured by a retaining clip 47. The lower end of the pendulum is provided with a downwardly facing C-shaped clamp 44c (shown in FIG. 4) for receiving and frictionally engaging a cylindrical magnet 48. As will be discussed, the magnet 48 functions both as a weight and as a means for indicating the position of the lower end of the pendulum.
Normally, as shown in FIG. 4, when the vehicle is traveling in a direction T and is not subjected to any deceleration or acceleration forces, the pendulum will be located in a resting position P r . As the towing vehicle brakes are applied and the towing vehicle is decelerated, the pendulum will swing outwardly in a forward direction D to a predetermined extended position P e , as determined by the magnitude of deceleration of the towing vehicle.
In order to reduce undesirable movement of the pendulum 44 when the sensing unit 30 is subjected to sudden forces other than deceleration such as road shock, for example, it is desirable to dampen the movement of the pendulum 44. It has been found that satisfactory damping can be achieved by locating a ferromagnetic element such as a metal channel 50 in spaced apart relationship with pendulum magnet 48. The metal channel 50 includes an arcuate lower wall 50a connected to a pair of spaced apart triangular shaped side walls 50b and 50c having apertures formed in the upper ends therefore for receiving the pivot pin 46. It has been found that the magnetic attraction between the pendulum magnet 48 and the surrounding metal channel 50 provides the necessary damping in the movement of the pendulum such that the road shocks transmitted to the pendulum 44 will not cause undesirable movement of the pendulum. Also, it has been found that the metal channel 50 shields the magnet 48 from external influencing or demagnetization forces.
The movement of the lower end of the pendulum relative to a normal vertical resting position is sensed by a detector means such as a Hall Effect device 52 spaced from and positioned adjacent one end 48a of the pendulum magnet 48. The Hall Effect device 52 is supported adjacent the magnet 48 within a square shaped opening 54a formed in a plastic carrier 54 seated within the metal channel 50. As the pendulum swings from the resting position P r , the Hall Effect device 52 is adapted to generate a voltage proportional to the amount of movement of the pendulum 44.
In accordance with the present invention, the deceleration sensing unit 30 includes means for providing a restoring force to the pendulum such that the pendulum can be returned to its resting position more rapidly than if gravity provided the sole restoring force. While it will be appreciated that various types of spring biasing means could be utilized to provide this function, it has been discovered that a separate magnet positioned in spaced apart relationship to the lower end of the pendulum 44 can be utilized to provide a restoring force which increases in magnitude as the pendulum swings further from its resting position. As shown in FIG. 4, a restoring magnet 56 is positioned near one end of the upper surface of the lower arcuate wall 50a of metal channel 50 and is supported thereon by a pair of spaced apart inverted U-shaped clips 54b provided in the plastic carrier 54. As the pendulum swings forwardly, the magnetic field of restoring magnet 56 will oppose the magnetic field of pendulum magnet 48 and a restoring force F r will oppose further forward movement of the pendulum in the direction D from the extended position P e . It has been found that providing such a restoring force to the pendulum of the deceleration sensing unit enhances the operator's controllability of the combined braking system.
In addition to supporting the Hall Effect device 52 and the restoring magnet 56, the plastic carrier 54 is also provided with an upwardly projecting stop means 54c (shown in FIG. 4) to limit the rearward swinging movement of the pendulum in the direction R. The stop means 54c is positioned a predetermined distance S from the center of the Hall Effect device 52 and, as will be discussed, prevents the user from adjusting the pendulum in a reverse direction.
In order to achieve proper operation, it is necessary that the resting position of the pendulum relative to the center of the Hall Effect device 52 be adjusted after the controller casing 31 has been securely mounted in the towing vehicle. The controller can be mounted under the vehicle dashboard, for example. This adjustment can be accomplished by leveling means 33. The leveling means 33 includes a sleeve member 33a for receiving the pivot pin 46. An inner lever arm 33b extends radially from the sleeve member 33a and has an outer end provided with an axially extending pin 33c which projects into an aperture 50d formed in the side wall 50b of the metal channel 50. The outer end of the sleeve member 33a, which is adapted to extend outwardly from the casing 31, is provided with an outer lever arm 33d.
In order to adjust the position of the Hall Effect device 52 relative to the pendulum 44, the lever arm 33d is pivoted about the pivot pin 46, thus causing the inner lever 33b and the pin 33c to pivot the metal channel 50 and the Hall Effect device 52. Typically, the retaining clip 47 is pressed sufficiently on the pin end 46b to cause the leveling means 33 and the metal channel 50 to be frictionally held relative to the plastic housing 42 about the pin 46, thus maintaining the adjusted position of the leveling means 33. The above adjustment is relatively simple, and consists of merely having the operator activate the controller on level ground by depressing the vehicle brake pedal, and then pivoting the outer lever arm 33d in a direction which causes relative movement of the pendulum in the direction D until the indicator light 38 just begins to light. If the operator were to accidently pivot the lever arm 33d in an opposite direction such that pendulum moves toward the stop means 54c, the stop means 54c prevents movement of the pendulum to a point which causes the indicator light 38 to turn on. Thus, the operator is prevented from adjusting the unit in the reverse direction.
In addition to adjusting the resting position of the pendulum 44 relative to the center of the Hall Effect device 52, another important adjustment is the spacing between the end wall 48a of the pendulum magnet 48 and the facing surface 52a of the Hall Effect device 52, as represented by dimension G in FIG. 3. Not only is the initial adjustment of the spacing G important, it is also important that this spacing be maintained during the swinging movement of the pendulum. To ensure that such spacing is maintained, the pendulum magnet is axially positioned in the C-shaped clamp 44c such that the distance between the one end 48a and the side wall 50c of the channel 50 is slightly less than the distance between the opposite end 48b and the side wall 50b. Thus, the magnetic attraction between the magnet 48 and the side wall 50c is slightly greater than the magnetic attraction between the magnet 48 and the side wall 50b. This causes the pendulum to be biased toward the side wall 50c such that the outer end of the bearing element 44b always remains in contact with the inner surface of the side wall 50c, while the outer end of the bearing element 44a is spaced from the inner surface of the side wall 50b.
It should be noted that, while the deceleration sensing unit of the preferred embodiment includes a pendulum mounted for pivotal movement about a generally horizontal axis, it will be appreciated that the deceleration sensing unit can utilize other types of mass movement sensing elements which, if desired, can be pivotally mounted about a vertical axis.
The circuit utilized to generate the electric brake control signal is shown in block diagram form in FIG. 5 and includes several unique features. Basically, the circuit utilizes a pulse width modulating (PWM) circuit 70 which receives a brake control signal representing the desired braking on a line 72 from an input circuit 74, and generates a square wave pulse train on a line 76 having a duty cycle directly proportional to the level of the brake control signal on the line 72. The modulated pulse train on the line 76 is then amplified to produce a brake driving signal on the line 14 to actuate the electric brakes.
The input circuit 74 receives a signal on a line 78 from a brake input signal generating means 80. The brake input signal generating means 80 can be a deceleration sensing unit of the type illustrated in FIGS. 2 through 4 which is adapted to generate a signal as a function of the deceleration of the towing vehicle. It will be appreciated that other types of deceleration sensing units could also be utilized with the circuit of the present invention. Also, the brake input signal generating means 80 can be a transducer (not shown) coupled to the hydraulic system of the towing vehicle for generating a signal proportional to the hydraulic pressure in the towing vehicle braking system, or a pressure transducer which is coupled to sense the pressure applied to the vehicle brake pedal by the driver. Such transducers are disclosed in U.S. Pat. No. 4,295,687, which is herein incorporated by reference.
The input circuit 74 also receives signals from the manual control 34 and the gain adjustment 36, whose functions have previously been discussed with reference to FIG. 1. However, it should be noted that, in the circuit of the present invention, the voltage level of the brake control signal on the line 72 represents the combination of the signals received from the brake control signal generating means 80 and the manual control 34. Thus, when the input circuit is generating a brake control signal on the line 72 at a predetermined level in response to a brake input signal received on the line 78 from the brake input signal generating means, actuation of the manual control 34 will increase the level of the brake control signal. In prior art systems, the brake control signal on the line 72 corresponded to the higher of the two signals supplied to the input circuit, and did not represent a combination of the two.
The PWM circuit 70 includes a sawtooth oscillator 80 which functions to generate a triangular shaped waveform on a line 82 as one input to a comparator 84. A second input of the comparator 84 is connected to receive the brake control signal on the line 72. When the level of the brake control signal on the line 72 is greater than the level of the triangular waveform on the line 82, the comparator 84 will generate a high level output signal such that a square wave signal will appear on the line 76. The duty cycle of the square wave PWM signal on the line 76 is directly proportional to the level of the brake control signal on the line 72.
When the vehicle brake pedal 25 is depressed, the stop light switch 26 supplies a power signal to a regulated power source 86 which generates a regulated voltage on a line 88 to activate the input circuit 74 and the PWM circuit 70. When the input circuit 74 and the PWM circuit 70 are activated, the PWM circuit 70 will generate a PWM output signal on the line 76.
Under normal operating conditions, the PWM output signal on the line 76 is supplied to the base of a transistor 90 having a collector coupled to supply the PWM output signal as an input to a current amplifier 92. However, before the output of the PWM circuit can be supplied to the current amplifier 92 through the transistor 90, a second transistor 94, having a collector connected to the emitter of the transistor 90 and an emitter connected to the circuit ground potential, must receive an enabling signal on a line 96 from the regulated power source 86. In accordance with the present invention, the enabling signal is only supplied to the transistor 94 when the voltage level supplied to the regulated power source 86 on the line 29 exceeds a predetermined level. Thus, in instances wherein, due to certain vehicle circuit problems, the stop light switch is not actuated and a lower level voltage signal may be inadvertently supplied to the regulated power source 86 on the line 29, the transistors 90 and 94 will remain in the off state and the output of the PWM circuit 70 will not be supplied to the current amplifier 92.
The output of the current amplifier 92 is generated on the line 14 which is connected to brake actuating coils 98 adapted to actuate the electromagnets 22 shown in FIG. 1. The indicator light 38 is connected to the line 14, and lights when a brake driving signal is present on the line 14. The intensity of the light 38 will be proportional to the average current level of the signal on the line 14.
The brake controller of the present invention includes a current sensing circuit 100 which receives a signal on a line 102 from the current amplifier 92 representing the current load on the brake output signal on the line 14. In the event the brake output current exceeds a predetermined level such as, for example, when a short is developed in one of the brake coils 98, the current sensing circuit 100 functions to reduce the level of the brake output current signal to the brake coils 98. In accordance with the present invention, the current sensing circuit 100 generates a limiting signal to the oscillator 80 on a line 104 which functions to progressively increase the overall level of the sawtooth waveform derived from the oscillator 80 on the line 82. This causes the duty cycle of the PWM on the line 76 to be progressively reduced, thus causing the output current level to be reduced.
FIGS. 6a, 6b, and 6c are waveform diagrams which can be used to summarize the operation of the circuit of FIG. 5. In FIGS. 6a and 6b the sawtooth oscillator 80 generates an output waveform 106 which oscillates between voltage levels VR1 and VR2. The waveform 106 will have a constant frequency which may be, for example, on the order of 400 Hz. to 600 Hz., although frequencies outside this range also may be used. The brake control voltage on the line 72 from the input circuit 74 is illustrated as a first constant voltage level 108a in FIG. 6a, and at a higher constant voltage level 108b in FIG. 6b. This would represent the condition where the driver initially applies a light force to the brake pedal and, subsequently, applies a heavier force to the pedal. When the input circuit 74 generates the lower level output voltage 108a, the voltage 108a will be above the output waveform 106 from the oscillator 80 only for short periods in each cycle. During these short periods, the comparator 84 generates relatively narrow pulses 110a (shown in FIG. 6a) which are applied to the current amplifier 92 through the transistor 90. As the voltage level of the brake control signal on the line 72 increases to the level 108b, as shown in FIG. 6b, it will be seen that the comparator 84 will have an output in the form of pulses 110b which have a greater width than the pulses 110a. Since the pulses are wider and there is no change in frequency, there is a greater duty cycle. Under a maximum braking condition, the width of the pulses 110b may increase until the comparator 84 applies a substantially constant voltage to the current amplifier 92 to fully actuate the towed vehicle brakes 16 and 17.
In the event that a partial short circuit occurs while the input circuit generates a brake control signal at the voltage 108b, the excessive current will cause the current sensing circuit 100 to generate a limiting signal on the line 104 to increase the voltage levels between which the waveform 106 oscillates such that, as shown in FIG. 6c, a waveform 106a, having a frequency similar to the waveform 106, oscillates between increased voltage levels VR3 and VR4, thus increasing the average voltage level of the waveform 106a as compared to the waveform 106. This causes the pulses 110b of FIG. 6b to be terminated short to produce reduced widths pulses 112 of FIG. 6c. By terminating the pulses 110b early, the duty cycle for the current amplifier 92 is shortened to limit the power dissipated by the components of the amplifier and, therefore, to protect the components from destruction. In the event of a total short circuit connecting the line 14 to ground, the level of the waveform 106 will be increased to a level wherein the current amplifier 92 remains substantially in the off state.
A preferred embodiment of the brake control circuit shown in FIG. 5 is illustrated in FIG. 7. In FIG. 7, the vehicle battery voltage (Vb) on the line 27a (from the power source 27 of FIG. 1) is supplied to the regulated power source 86 through the closing of either the stop light switch 26 or the closing of a single pole switch 34a included in the manual control 34. The regulated power source 86 includes a resistor 120 connected between the line 29 and the Vcc output line 88. A capacitor 122 connected between the line 88 and the circuit ground potential charges to a voltage level Vcc determined by the breakdown voltage of a zener diode 124. The zener diode 124 has a cathode connected to the line 88 and an anode connected to the base of the transistor 94. Both the regulated voltage Vcc and the vehicle battery voltage Vb are utilized to power various portions of the circuit.
Normally, when either the stop light switch 26 or the manual control switch 34a is closed, a Vb power signal is supplied to the regulating circuit 86 on the line 29 and, when the switches are open, the line 29 will be at the circuit ground potential. When a voltage level Vb is present on the line 29, the diode 124 will conduct and generate an enabling signal on the line 96 to turn on the transistor 94. As previously mentioned, this enables the transistor 90 to couple the output pulses of the PWM circuit to the current amplifier 92. However, in the event the switches 26 and 34a are open and the line 29 is at a voltage level above the circuit ground potential such as, for example, if there is a circuit problem in the stop light circuit such as an insufficient ground, the diode 124 will not conduct if the voltage is below the breakdown level of the diode, and the transistor 94 will remain in the off state. This prevents the controller from generating a brake output signal when either the stop light switch 26 or the manual switch 34a has not been actuated.
In the circuit of FIG. 7, the brake input signal generating means 80 is shown as the Hall Effect device 52 incorporated in the deceleration sensing unit 30 of FIGS. 2 through 4. The Hall Effect device 52 includes a power supply terminal 52-1 connected to receive a reduced level Vcc signal through a resistor 125 and a ground terminal 52-2 connected to the circuit ground. The output 52-3 of the Hall Effect device is connected to the line 78 which is supplied to the input circuit 74. The Hall Effect device 52 can be a Model No. UGN-3503U available from Sprague Electric Co. of Concord, N.H.
Basically, the input circuit 74 consists of a two transistor, common emitter bridge circuit which functions to generate a voltage on the line 72 to the PWM circuit 70 at a level representing the desired amount of braking. The input circuit 74 includes a first transistor 126 having a base connected to receive the output of the Hall Effect device 52 through a resistor 128. The emitter of the transistor 126, along with the emitter of a second transistor 130, are connected to the circuit ground potential through a resistor 132. Normally, when no deceleration is being sensed by the deceleration sensing unit and the pendulum 44 is in the resting position, the output of the Hall Effect device 52 on the line 78 is such that the transistor 126 is in the off state and just at a point to turn on.
The transistor 130 is normally biased in the on state by resistors 134 and 136 connected in series between the Vcc potential and the circuit ground potential. The base of the transistor 130 is connected to the junction of the resistors 134 and 136. When the transistor 130 is in the on state, current flows from the Vcc voltage source through the resistor 125 and a potentiometer 34b through the transistor 130 and to the circuit ground through the resistor 132. The potentiometer 34b operates in conjunction with the switch 34a as the manual slide control 34 of FIG. 1. The voltage level at the variable terminal of the potentiometer 34b appears on the line 72 as the brake control signal. A filter capacitor 140 is connected between the line 72 and the base of the transistor 130. The gain adjustment 36 of FIGS. 1 and 5 is shown in FIG. 7 as a potentiometer 36a connected between the collector of the transistor 126 and the junction between the resistor 125 and the potentiometer 34b.
Normally, when the deceleration sensing unit 30 is not subjected to any deceleration, the pendulum magnet 48 is positioned relative to the Hall Effect device 52 such that the output voltage on the line 78 is just below the voltage level required to turn on the transistor 126. At this time, the voltage level of the brake control signal on the line 72 is such that when, either the stop light switch 26 or the manual switch 34a is closed, the PWM circuit generates the output signal on the line 76 with approximately a 5% duty cycle. As deceleration is sensed by the deceleration sensing unit 30, the voltage output of the Hall Effect device 52 on the line 78 will increase to a level substantially proportional to the magnitude of deceleration of the associated vehicle. As the voltage level on the line 78 increases, the transistor 126 will turn on and current will flow through the gain adjustment potentiometer 36a and the transistor 126. As the transistor 126 begins to turn on, the transistor 130 begins to turn off and the voltage level of the brake control signal on the line 72 increases. This causes the duty cycle of the output of the PWM circuit 70 to increase. In the event additional braking is required, the operator can actuate the manual slide control 34 to move the variable terminal of the potentiometer 34 to further increase the voltage level on the line 72.
The basic component of the PWM circuit 70 shown in FIG. 5 is an LM 556 dual timer integrated circuit 142 available from National Semiconductor. The right hand portion of the circuit 142 includes a pair of internal comparators 144 and 145 having inputs connected to selected terminals of the circuit 142. The outputs of the comparators are connected to an internal flip flop 146 having an output supplied to output terminal 142-9 of the circuit 142. The left hand portion of the circuit 142 is identical to the right hand portion and includes a pair of comparators 147 and 148 and a flip flop 149. The reset terminals (142-4 and 142-10) of the flip flops 146 and 149 are connected to the Vcc power supply. Basically, the right half of the integrated circuit 142, as viewed in FIG. 7, is utilized in conjunction with an external resistor/capacitor network as the oscillator 80 of FIG. 5 to produce a sawtooth waveform at a predetermined frequency on the line 82, while the comparator 147 and the flip flop 149 of the left hand portion of the circuit 142 are utilized as the comparator 84 to produce the PWM output signal on the terminal 142-5. The comparator 148 is not used.
A resistor 150 and a capacitor 151 are connected in series between the output 142-9 of the internal flip-flop 146 and the circuit ground potential. The voltage developed across the capacitor 151 is applied to terminals 142-8 and 142-12 as an input to the comparators 145 and 144 respectively. The other inputs to the comparators are connected together through a filter capacitor 152 to ground. Each comparator compares the voltage across the capacitor 151 with a separate internal reference voltage, which can be a selected portion of the control voltage Vcc, as determined by an internal voltage divider (not shown). Therefore, when the voltage across the capacitor 151 drops below a certain first percentage of the control voltage Vcc, an output from the comparator 145 will be supplied as one input to the flip flop 146 and cause the flip flop 146 to produce a high level voltage signal at terminal 142-9. Similarly, when the voltage across the capacitor 151 exceeds a certain second percentage of the control voltage Vcc, the output of the second comparator 144 will be supplied to the other input of the flip flop 146 and cause the flip flop 146 to produce a low voltage signal at the terminal 142-9. With these inputs from the comparators 144 and 145, the flip flop 146 will develop an output with a rectangular waveform which is supplied to the capacitor 151 through the resistor 150. Consequently, there will be developed across the capacitor 151 a triangular shaped sawtooth waveform, having a frequency determined by the component values of the resistor 150 and the capacitor 151.
A second resistor and capacitor network consisting of a resistor 153 and a capacitor 154 have component values similar to the resistor 150 and the capacitor 151 such that the rectangular voltage waveform at the terminal 142-9 is supplied to the capacitor 154 through the resistor 153 and a second triangular waveform similar to the waveform across a capacitor 151 is also produced across the capacitor 154. This second triangular waveform is supplied on the line 82 to the terminal 142-2 of the circuit 142 as an input to the comparator 147. As will be discussed, a second triangular waveform identical to the first triangular waveform is produced since, in the event of a partial or full short circuit condition, the average voltage level of the second triangular waveform is increased, thereby reducing the duty cycle of the PWM signal on the line 76. If the first triangular waveform across the capacitor 151 was increased in this manner, the operation of the oscillator 80 would be adversely affected.
The other input of the comparator 147 is connected to receive the brake control voltage on the line 72 from the input circuit 74. When the control voltage from the input circuit 74 is greater than the level of the triangular waveform on the line 82, the comparator 147 generates a high level output signal to set the internal flip flop 149. This causes the flip flop 149 to generate a rectangular waveform at the terminal 142-5 having a duty cycle directly proportional to the level of the control voltage at terminal 142-3. This rectangular waveform at the terminal 142-5 is supplied through a resistor 141 to the transistor 90 on the line 76.
When a PWM signal appears on the line 76 to the transistor 90, and the transistor 94 is in the on state, the PWM signal will be coupled to the current amplifier 92. The PWM signal is supplied through a resistor 155 to the base of a transistor 156 having an emitter connected to the Vb power supply. A resistor 158 is connected between the emitter and the base of the transistor 156. A zener diode 159 has an anode connected to the ground potential and a cathode connected to the base of the transistor 156. The zener diode 159 has a breakdown voltage greater than the voltage Vb and is utilized to protect the current amplifier transistors from high level voltage spikes generated in the vehicle electrical system.
The PWM signal supplied to the base of the transistor 156 is coupled to the base of a second amplifier transistor 160 which provides the main current path between the Vb power supply and the output line 14 to the brake actuating coils 98. A filter capacitor 161 is connected between the base of the transistor 160 and the output line 14, while a resistor 162 is connected between the base and the emitter of the transistor 160.
A resistor network 163 consisting of a plurality of parallel connected resistors 163a, 163b, and 163c, each of a very low value, are connected between the Vb power supply and the collector of the output transistor 160. Because the value of each of the resistors in the network 163 is relatively low, the voltage difference across the resistors will be relatively small.
In the present invention, the current sensing circuit is adapted to sense this voltage difference and, in the event the voltage difference exceeds a predetermined amount, generates a limiting signal on the line 104 to the PWM circuit 70. The voltage level on the output line 102 of the current amplifier 92 is supplied to the base of a transistor 164 through a resistor 165. A filter capacitor 166 is connected between the base of the transistor 164 and the Vb power supply. When the voltage level on the line 102 reaches a predetermined point, the transistor 164 will turn on and begin to charge a capacitor 167 connected between the collector of the transistor 164 and the circuit ground. The voltage across the capacitor 167 is supplied to the line 104 through a resistor 168 to charge the capacitor 154. This causes the average voltage level of the sawtooth waveform on the line 82 to increase, thus reducing the duty cycle of the PWM output pulses supplied to the current amplifier. When the voltage level on the line 102 to the current sensing circuit 100 falls such that the transistor 164 turns off, the capacitor 167 will discharge on the line 82 and the triangular waveform will return to its original level.
The brake driving signal generated on the line 14 is applied to one or more brake actuating coils 98. When a braking signal is present on the line 14, current flows through a resistor 170 and a LED 172 which lights to indicate to the driver that braking current is being supplied. A resistor 174 connected between the output lines 14 and the circuit ground potential prevents the diode 172 from lighting when the brake controller is off and there is a minimal current leakage through the transistor 160 and other external vehicle wiring.
When braking current from the transistor 160 turns off, a diode 175 provides a current path to continue the flow of inductive current through the brake coils 98. During short duration operation, which is with low braking current, the current through the diode 175 will cease before the next pulse because the energy is consumed by the resistance of the coils 98. However, during long on time operation, which is with high braking current, current flows through the diode 175 until the transistor turns on again. This feature avoids damaging the transistor 160 and other components in the amplifier 92 from inductive voltage spikes.
In accordance with the provisions of the patent statutes, the principle and mode of operation of the invention have been illustrated and described in what is considered to represent its preferred embodiment. However, it should be understood that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope.
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The present invention relates to a self-contained electric brake controller for energizing electrically operated brakes in a towed vehicle in response to a demand by a driver in a towing vehicle. The controller includes a unique deceleration sensing unit for generating a signal proportional to the magnitude of deceleration of the towing vehicle. The deceleration sensing unit includes an outer housing adapted to be secured relative to the towing vehicle, and a pendulum mounted on an axis for pivotal movement relative to the housing. The pendulum is movable in one direction from a resting position to a predetermined extended position when the vehicle is subjected to a predetermined magnitude of deceleration. The pendulum includes a magnet spaced from the pivot axis of the pendulum. A detector such as a Hall Effect device is carried by the housing and is responsive to the magnetic field produced by the pendulum magnet for generating a position signal representing the predetermined extended position of the pendulum. This position signal corresponds to the predetermined magnitude of deceleration of the vehicle. The deceleration sensing unit includes a second magnet carried by the housing and spaced from the pendulum for producing a magnetic field which, as the pendulum swings to its extended position, opposes the magnetic field of the pendulum magnet to produce a restoring force to resist further forward movement of the pendulum. The deceleration sensing unit also includes a damping element constructed of a ferromagnetic material spaced from the pendulum magnet for damping undesirable movement of the pendulum. Also, the circuit responsive to the deceleration signal includes several unique features.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119 to U.S. Provisional Application Ser. No. 62/155,135, filed Apr. 30, 2015, the entirety of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present disclosure pertains to openers.
BACKGROUND
[0003] A wide variety of openers have been developed. Of the known openers, each has certain advantages and disadvantages. There is an ongoing need to provide alternative openers as well as alternative methods for manufacturing and using openers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] The disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings, in which:
[0005] FIG. 1 is a perspective view of an example opener.
[0006] FIG. 2 is a top view of an example opener.
[0007] FIG. 3 is a bottom view of an example opener.
[0008] FIG. 4 is a side view of an example opener.
[0009] FIG. 5 is a side view of an example opener.
[0010] FIG. 6 is a perspective view of an example opener.
[0011] FIG. 7 is a top view of an example opener.
[0012] While the disclosure is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the disclosure to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure.
DETAILED DESCRIPTION
[0013] For the following defined terms, these definitions shall be applied, unless a different definition is given in the claims or elsewhere in this specification.
[0014] All numeric values are herein assumed to be modified by the term “about,” whether or not explicitly indicated. The term “about” generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In many instances, the terms “about” may include numbers that are rounded to the nearest significant figure.
[0015] The recitation of numerical ranges by endpoints includes all numbers within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
[0016] As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0017] The following detailed description should be read with reference to the drawings in which similar elements in different drawings are numbered the same. The drawings, which are not necessarily to scale, depict illustrative embodiments and are not intended to limit the scope of the disclosure.
[0018] A variety of containers exist for the packaging of consumer liquids, beverages and/or drinks. In some instances, the container and/or packaging includes a two-piece system including a cap (e.g. twist off) coupled to a bottle. Further, in some instances, a unitary sheet of foil and/or a plastic seal may extend around both the cap and the bottle. In order to remove the cap, a user may have to cut, slice and/or tear the seal to disengage the cap from the bottle. In some instances, it may be desirable to grip and twist the cap and foil seal with sufficient force such that both the cap and the seal are removed from the bottle at the same time. For example, in some instances it may be desirable to remove both the seal and the cap of a 5-HOUR ENERGY™ drink and/or other similar energy drinks or the like. In particular, the twist cap of a miniature energy drink bottle may be sufficiently small (e.g., having a diameter less than about 1 inch or about 0.875±0.1 inches) such that it may be difficult for a user to easily use their hands to twist off the cap. In other words, the size of the twist cap and the force required to twist a cap of such dimensions may require a reasonably high amount of force, making it challenging to open the bottle while simultaneously cutting the plastic seal around the bottle cap. Therefore, it may be desirable to utilize materials and/or design a dual combination opener that can both cut a foil/plastic seal and remove a bottle cap simultaneously.
[0019] FIG. 1 is a schematic view of an example dual combination cutting and twisting opener 10 . Opener 10 may be a unitary body that includes opener body portion 14 coupled to gripping arms 12 A and 12 B. Gripping arms 12 A and 12 B may extend away from body portion 14 . Further, one or more attachment members 24 may extend away from gripping arm 12 A and/or 12 B. Opener 10 may include an interior surface 28 which includes the interior surface of gripping arms 12 A, 12 B and body portion 14 . Similarly, opener 10 may include an exterior facing surface 30 defined by an exterior surface of gripping arms 12 A, 12 B and body portion 14 .
[0020] Body portion 14 may include curved body wall 20 . As stated above, interior surface 28 may extend along and be partially defined by the inner surface of the body wall 20 . In some instances, body wall 20 may include one or more cap gripping surfaces 16 . Cap gripping surface 16 may include projections, textures, ridges, ribs, grooves, channels, cuts, notches, flutes or the like extending along a portion or all of interior surface 28 .
[0021] As shown in FIG. 1 , cap gripping surface 16 may extend from a bottom surface 38 (shown in FIG. 3 ) to a top surface 36 of interior surface 28 of body portion 14 . In other words, it is contemplated that in some embodiments gripping surface 16 may extend the entire “thickness” of body portion 14 . Gripping surface 16 may be designed to be able to grip a variety of materials. For example, gripping surface 16 may designed to grip and/or embed in a variety of polymer or metallic materials. The ability to grip and/or embed in a variety of materials may allow a user to more easily apply leverage via opener 10 to twist and remove a bottle cap, for example. This may also make it easier to twist and remove a bottle cap while simultaneously cutting a seal disposed around the bottle cap.
[0022] In some instances, body portion 14 may include one or more teeth members 18 . As shown in FIG. 1 , teeth members 18 may be positioned and aligned along the bottom surface 38 (e.g. the bottom “edge”) of body 14 . Further, teeth 18 may extend along a portion or all of the interior surface 28 . Teeth members 18 may project away from interior surface 28 .
[0023] It is contemplated that teeth members 18 may be a variety of shapes. For example, teeth 18 illustrated in FIGS. 1-3 may bear some resemblance to the shape of a shark fin or, similarly, the teeth of a circular saw blade. In other words, an individual tooth 18 may extend away from interior surface 18 and project to a “tip” or “point.” Further, it is contemplated that teeth 18 may assume a variety of shapes. For example, teeth 18 may be square, triangular, hooked, angled, rounded, beveled, scalloped, pegged, slanted or the like.
[0024] While the above discussion described teeth 18 as being positioned along the bottom edge of body 14 , it is contemplated that teeth 18 may be positioned at other locations along interior surface 28 . For example, teeth 18 may be positioned along a top edge, the middle portion or dispersed intermittently along interior surface 28 . As described above, the alignment of multiple teeth 18 permits opener 10 to cut and/or slice a foil or plastic seal, for example, as opener 10 is twisted to simultaneously remove cap (discussed above).
[0025] As shown in FIGS. 1 and 2 , curved body wall 20 may define a central opening 26 . As shown in FIG. 2 , central opening 26 may be substantial circular and include an inner radius identified in FIG. 2 as dimension “X 1 .” In some embodiments, radius X 1 may be about 0.3-0.6 inches, or about 0.4-0.5 inches, or about 0.483 inches.
[0026] Additionally, body portion 14 may include an outer radius identified in FIG. 2 as dimension “X 2 .” In some embodiments, radius X 2 may be about 0.4-0.8 inches, or about 0.6-0.7 inches, or about 0.683 inches.
[0027] Central opening 26 may be sized to accept a variety of cap sizes and configurations. Central opening 26 may define a portion of an arc or circle. For example, as shown in FIG. 2 , central opening 26 extends approximately 270 degrees of a complete circle. It is contemplated that circular opening 26 could extend more or less than the partial circle shown in FIG. 2 , depending on the particular application that the opener was designed to accommodate.
[0028] As shown in FIGS. 1 & 2 , body portion 14 may be coupled to gripping arms 12 A and 12 B. Gripping arms 12 A and 12 B may be substantially parallel to one another. In particular, interior surface 28 of gripping arms 12 A and 12 B may be substantially parallel (as shown in FIG. 2 ). By contrast, the exterior surface 30 of gripping arms 12 A and 12 B may widen (e.g. flare) from the point at which gripping arms 12 A and 12 B are coupled to body portion 14 to the end of the gripping arm 12 A/ 12 B.
[0029] Gripping arms 12 A & 12 B may include a finger gripping surface 22 (shown in FIGS. 1, 4 and 5 ). In some embodiments, finger gripping surface 22 may be substantially similar to the gripping surface describe above with respect to cap gripping surface 16 . For example, finger gripping surface 22 may include projections, textures, ridges, ribs, grooves, channels, cuts, notches, flutes or the like extending along a portion or all of exterior surface 30 . Exterior surface 30 may include an ergonomic shape. The ergonomic shape may be one that follows the contours of a user's finger.
[0030] Additionally, FIGS. 1 & 2 show an attachment member 24 extending from and end of gripping arm 12 A. While FIGS. 1 & 2 show attachment member extending from gripping arm 12 A, it is contemplated that attachment member may extend from gripping arm 12 B or any other portion of opener 10 . In some instances, attachment member may allow opener 10 to be coupled, clipped and/or attached to a key ring or the like. As shown, attachment member includes an attachment opening 42 . Attachment opening 42 may be sized to permit a variety of different size key rings, etc. to attach to opener 10 . While shown as a circle in FIGS. 1 & 2 , it is contemplated that attachment opening 42 may include other shapes. For example, attachment opening 42 may be a triangle, oval, or the like.
[0031] FIG. 3 shows bottom view of opener 10 . Opener 10 may include one or more cavities 40 . Cavities 40 may be defined as voids, recesses, etc. in which material is removed from opener 10 . As shown in FIG. 3 , cavities 40 may be separated from one another. For example, FIG. 3 shows four independent cavities 40 .
[0032] FIGS. 4 & 5 show side views of opener 10 . As shown in each of FIGS. 4 & 5 , finger gripping surfaces 22 may extend along a portion of the exterior surface 30 of opener 10 .
[0033] In some instances, removing the cap and foil seal of a bottle simultaneously may include inserting the cap (along with the foil seal) into central opening 26 . In some instances, the thickness of the opener 10 may be designed such that when the cap is inserted into central opening 26 , teeth 18 may be aligned with the bottom of the cap. In other instances, teeth 18 may be aligned at a different location. After inserting the cap into central opening 26 , a user may then “squeeze” gripping arms 12 A & 12 B such that gripping arms move toward each another. The movement of gripping arms toward one another may reduce the radius of central opening 26 . This reduction in radius may effectively “tighten” opener 10 around an example cap. Once tightened, a user may spin the “ungripped” portion of the example container (e.g. bottle). Opener 10 , through the gripping action of gripping surface 16 and the cutting action of teeth 18 , may then effectively hold the cap stationary while the remainder of the container is twisted relative to the cap. This action may not only untwist the cap, but may also simultaneously cut the foil seal at the location where teeth 18 are aligned.
[0034] Dimensions of opener 10 (as shown in FIGS. 1-5 ) may include a length of about 1-5 inches, or about 2-3 inches, or about 2.718 inches. The opening may have a width of about 0.5-1.5 inches, or about 0.6-1 inches, or about 0.8 inches. The width across arms 12 A/ 12 B may be about 1-4 inches, or about 1.5-2.5 inches, or about 2.146 inches. The height of opener 10 may be about 0.2-0.8 inches, or about 0.3-0.5 inches, or about 0.4 inches. These are just examples.
[0035] FIGS. 6-7 shows an alternative opener 110 . As shown, opener 110 may include a secondary opening 144 . As shown, secondary opening 144 may be positioned adjacent to central opening 126 . Secondary opening 144 may be similarly designed and perform substantially similar to central opening 126 . For example, secondary opening 144 may include secondary gripping surface 146 . Secondary gripping surface 146 may be similar to cap gripping surface 116 .
[0036] Opening 126 may be sized to include a radius X 1 of about 0.3-0.6 inches, or about 0.4-0.5 inches, or about 0.483 inches (e.g., similar to what is shown in FIG. 2 ). Secondary opening 144 may include a radius “Y”. In some embodiments, radius Y may be about 0.3-0.8 inches, or about 0.5-0.7 inches, or about 0.600 inches.
[0037] In some instances, radius “Y” may be larger than the radius “X 1 ” of central opening 126 . It is contemplated that secondary opening 144 may be sized to facilitate the removal of caps different in diameter to that of the caps designed to be removed by central opening 126 . For example, secondary opening 144 may be sized to remove the caps of a larger bottle (e.g. water bottle, soda, beer, etc.). In other instances, radius “Y” may be the same size or smaller than the radius “X 1 ”. Secondary opening 144 may include a gripping surface. In some of these and in other instances, secondary opening 144 may include teeth (not shown), similar to teeth 18 . Alternatively, secondary opening 144 may be free of teeth and, instead, may only include the gripping surface for gripping the cap of a bottle.
[0038] Opener 110 and/or other components of opener 110 may be made from a metal or polymer (some examples of which are disclosed below), a metal-polymer composite, combinations thereof, and the like, or other suitable material.
[0039] Dimensions of opener 110 (as shown in FIG. 6 ) may include a length of about 1-5 inches, or about 2-3 inches, or about 2.718 inches. The opening may have a width of about 0.5-1.5 inches, or about 0.6-1.2 inches, or about 0.996 inches. The width across arms 12 A/ 12 B may be about 1-4 inches, or about 1.5-2.5 inches, or about 2.146 inches. The height of opener 110 may be about 0.2-0.8 inches, or about 0.3-0.5 inches, or about 0.4 inches. The distance between the center of opening 126 and opening 144 may be about 0.5-2.5 inches, or about 1-1.5 inches, or about 1.25 inches. These are just examples.
[0040] Opener 10 and 110 described herein may be made from a polymer or other suitable material. Some examples of suitable polymers may include polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), fluorinated ethylene propylene (FEP), polyoxymethylene (POM, for example, DELRIN® available from DuPont), polyether block ester, polyurethane (for example, Polyurethane 85A), polypropylene (PP), polyvinylchloride (PVC), polyether-ester (for example, ARNITEL® available from DSM Engineering Plastics), ether or ester based copolymers (for example, butylene/poly(alkylene ether) phthalate and/or other polyester elastomers such as HYTREL® available from DuPont), polyamide (for example, DURETHAN® available from Bayer or CRISTAMID® available from Elf Atochem), elastomeric polyamides, block polyamide/ethers, polyether block amide (PEBA, for example available under the trade name PEBAX®), ethylene vinyl acetate copolymers (EVA), silicones, polyethylene (PE), Marlex high-density polyethylene, Marlex low-density polyethylene, linear low density polyethylene (for example REXELL®), polyester, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate, polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), poly paraphenylene terephthalamide (for example, KEVLAR®), polysulfone, nylon, nylon-12 (such as GRILAMID® available from EMS American Grilon), perfluoro(propyl vinyl ether) (PFA), ethylene vinyl alcohol, polyolefin, polystyrene, epoxy, polyvinylidene chloride (PVdC), poly(styrene-b-isobutylene-b-styrene) (for example, SIBS and/or SIBS 50A), polycarbonates, ionomers, biocompatible polymers, other suitable materials, or mixtures, combinations, copolymers thereof, polymer/metal composites, and the like.
[0041] Forming the openers disclosed herein may include a molding (e.g., injection molding), casting, 3-D printing, or other suitable processes.
[0042] It should be understood that this disclosure is, in many respects, only illustrative. Changes may be made in details, particularly in matters of shape, size, and arrangement of steps without exceeding the scope of the disclosure. This may include, to the extent that it is appropriate, the use of any of the features of one example embodiment being used in other embodiments. The invention's scope is, of course, defined in the language in which the appended claims are expressed.
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Openers for opening a twist cap of a bottle while simultaneously cutting a seal adjacent the twist cap are disclosed. An example opener may include a body a first arm and a second arm projecting therefrom. The body may have an inner curved surface. The first arm and the second arm may be designed to be moved closer to one another during use of the opener. A first gripping region may be defined along the inner curved surface. The first gripping region may be designed to engage and grip the twist cap during use of the opener. A plurality of cutting members may be positioned along the inner curved surface. The cutting members may be designed to pierce and cut the seal during use of the opener.
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FIELD OF THE INVENTION
[0001] The invention relates to delivery of particulate material to a location below ground. A significant application is as part of a method of hydraulic fracturing of a subterranean reservoir formation, placing proppant in the fracture so as to keep the fracture open as a flow path. However, the invention also extends to other applications where placing of particulate material underground, notably within subterranean reservoirs, is required. It is envisaged that the invention will be used in connection with exploration for, and production of, oil and gas.
BACKGROUND OF THE INVENTION
[0002] Placing particulate material at a location below ground is a very significant part of a hydraulic fracturing operation. It may also be done in the context of various other operations carried out on underground wells including placing a gravel pack when completing a well. Hydraulic fracturing is a well established technique for reservoir stimulation. Fluid is pumped under pressure into a subterranean formation, forcing portions of the formation apart and creating a thin cavity between them. When pumping is discontinued the natural pressure in the subterranean formation tends to force the fracture to close. To prevent the fracture from closing completely it is normal to mix a solid particulate material (termed a proppant) with the fracturing fluid at the surface and use the fluid to carry the proppant into the fracture. When the fracture is allowed to close, it closes onto the proppant and a flow path to the wellbore between the proppant particles remains open. The proppant is then under considerable pressure from the formation rock pressing on it.
[0003] When the proppant is mixed with the fracturing fluid at the surface and pumped into the wellbore it is subjected to very high shear. The proppant-laden fluid then flows down the wellbore under conditions of lower shear. Subsequently it turns and flows out of the wellbore and into the fracture in the formation. Entry to the fracture may be associated with an increase in shear, in particular if the wellbore is cased and the fluid passes through perforations in the wellbore casing to enter the fracture. Once the fluid enters the fracture, and as the fracture propagates and extends into the reservoir, the fluid is subjected to much less shear. Suspended solid begins to settle out. Subsequently pumping is discontinued, allowing the fracture to close onto the proppant packed in the fracture.
[0004] In order that the fluid can convey particulate material in suspension, and place it across the fracture face, it is conventional to include a viscosity-enhancing thickening agent in the fluid. Typically the fluid is then formulated so as to achieve a viscosity of at least 100 centipoise at 100 sec −1 at the temperature of the reservoir. Guar is widely used for this purpose. Guar derivatives and viscoelastic surfactants may also be used. However, for some fracturing operations, especially where the rock has low permeability so that leak off into the rock is not a significant issue, it is preferred to pump a fluid, often called “slickwater”, which is water or salt solution containing a small percentage of friction reducing polymer which does not significantly enhance viscosity as much as a thickening agent such as guar. The fluid then has low viscosity. This considerably reduces the energy required in pumping but keeping particulate material in suspension becomes much more difficult and a higher pump flow rate is commonly used.
[0005] As recognized in Society of Petroleum Engineers Papers SPE98005, SPE102956 and SPE1125068 conventional proppant particles suspended in slickwater pumped into a large fracture will settle out more quickly than is desired and form a so-called “bank” or “dune” close to the wellbore. Because of this premature settling, proppant may not be carried along the fracture to prop the full length of the fracture and proppant may not be placed over the full vertical height of the fracture. When pumping is stopped and the fracture is allowed to close, parts of the fracture further from the wellbore may not contain enough proppant to keep them sufficiently open to achieve the flow which would be desirable As a result, the propped and effective fracture size may be less than the size created during fracturing.
[0006] One approach to improving the transport of particulate proppant has been to use a material of lower specific gravity in place of the conventional material which is sand or other relatively heavy mineral (sand has a specific gravity of approximately 2.65). Society of Petroleum Engineers paper SPE84308 describes a lightweight proppant having a specific gravity of only 1.75 which is a porous ceramic material coated with resin so that pores of the ceramic material remain air-filled. This paper also describes an even lighter proppant of specific gravity 1.25 which is based on ground walnut hulls. This is stated to be a “resin impregnated and coated chemically modified walnut hull”.
[0007] These lightweight proppants are more easily suspended and transported by slickwater and their use is further discussed in SPE90838 and SPE98005, the latter paper demonstrating that settling out is reduced compared to sand, although not entirely avoided.
[0008] There have been a number of other disclosures of proppants lighter than sand. For example U.S. Pat. No. 4,493,875 (3M) describes a novel proppant consisting of composite particles, the core of which is a conventional particle such as silica sand and the coating or shell of which is a thin void-containing layer such that the overall density of the composite particle approaches that of the fracturing fluid. Preferably, the coating/shell comprises hollow glass microspheres embedded in an adhesive which bonds to the core.
[0009] US patent application 2008/277,115 A1 (Rediger et al., Georgia-Pacific Chemicals, Inc.) also describes a composite proppant which is a porous ceramic or a silica sand coated with a low density material (e.g. cork particles) which is bound to the substrate using a Novolac resin crosslinked with hexamine—the resultant example proppants have specific gravities in the range 1.94-2.37 kg/m 3 .
[0010] U.S. Pat. No. 7,491,444 (Oxane Materials, Inc.) describes a process for making proppant particles by creating a shell around a template particle which may be hollow. The particles have specific gravities in a range extending to less than 1.0.
[0011] US2005/096207 and US2006/016598 (Thomas Urbanek) describe processes for making low density ceramic proppant particles. The products are claimed to have a specific gravity as low as 1.0 in the second of these documents.
[0012] A recognized issue with lightweight proppants is that they may not be as strong as sand and are at risk of becoming partially crushed when a hydraulic fracture is allowed to close on the proppant placed within it. An approach to the suspension of particulate proppant which has recognized this issue is disclosed in US2007/015669, also in WO2009/009886 and in “Lightening the Load” New Technology Magazine, January/February 2010 pages 43 and 44. According to the teachings of these documents, a conventional proppant such as sand is treated to render its surface hydrophobic and is added to the slurry of proppant and water. Bubbles adsorb to the hydrophobic solid particles so that the adsorbed gas gives the particles a lower effective density. The literature describing this approach advocates it on grounds that the conventional sand is both cheaper and stronger than lightweight proppant.
SUMMARY OF THE INVENTION
[0013] According to one aspect of the present invention there is provided a wellbore fluid comprising an aqueous carrier liquid and first and second hydrophobic particulate materials suspended therein, where the first hydrophobic particles have a higher specific gravity than the second hydrophobic particles, the fluid also comprising a gas to wet the surface of the particles and bind them together as agglomerates.
[0014] In a second aspect the invention provides a method of delivering particulate material below ground, comprising supplying, underground, a composition comprising an aqueous carrier liquid in which there are suspended at least two particulate materials which are hydrophobic, where a first one of these materials has a higher specific gravity than a second one, the fluid also comprising a gas wetting the surface of the particles and binding the particles together such that agglomerates of the particulate materials held together by the gas are present below ground.
[0015] In some embodiments of this invention the delivery below ground is done in the course of fracturing a reservoir formation. This may be a gas reservoir and the fracturing step may be followed by producing gas, gas condensate or a combination of them from the formation through the fracture and into a production conduit in fluid communication therewith.
[0016] Agglomeration may be prevented or reversed when-the composition is subjected to shear. As already mentioned a composition which is pumped downhole is subjected to varying amounts of shear in the course of the journey downhole. Consequently agglomeration may take place at the subterranean location to which the particulate material is delivered. However, it is possible that agglomeration may take place or commence in the course of flow towards the subterranean location where the material will serve its purpose.
[0017] It will be appreciated that the present invention makes use of two materials which are particulate in the sense that each of them is present as many small particles and uses them to serve two purposes. The first particulate material is a material which it is desired to place at a subterranean location. In significant forms of this invention it serves as a proppant placed in a hydraulic fracture. The second particulate material aids transport by assisting suspension in the carrier fluid. The agglomerates will contain both the denser first particles and the lighter second particles. The presence of the lighter particles helps to reduce the density of the agglomerates, which is beneficial because agglomerates of lower density will settle out of the carrier liquid more slowly and as a result they can be transported more effectively to their intended destination.
[0018] The presence of gas in the agglomerates of hydrophobic particles also reduces their overall density. This is consistent with the teaching of prior documents to utilize adsorbed gas to enhance buoyancy. However, we have found that the volume of gas which can be incorporated into stable agglomerates is limited and may not reduce the effective density to the extent which might be hoped for. Secondly, when a particulate material is made lighter by means of adsorbed gas, that gas will be compressed by the increasing hydrostatic pressure as it is pumped downhole into a fracture. The volume occupied by gas will thus be reduced relative to the particulate material. Consequently, the volume of gas which must be supplied at the surface, in order to provide a desired volume of gas downhole, may be large.
[0019] When both lighter and denser particulates are agglomerated with gas, in accordance with this invention, the overall density of the particulates may be lower than would be achievable without the lighter particulate material. Secondly a smaller volume of gas may be required in order to achieve the desired reduction of density under downhole hydrostatic pressure. Nevertheless it should be appreciated that when agglomerates are formed in accordance with this invention the amount of gas contained in them may be less than the maximum possible
[0020] Inhibiting the settling out of particulate material allows it to be transported more effectively to its intended destination. In the context of hydraulic fracturing the length and/or vertical height of fracture (i.e. the fracture area) which remains propped open after pumping has ceased is greater than would be possible if only the first particulate material was present. The compositions used in this invention may be formulated such that the resulting agglomerates formed in accordance with this invention have a density not exceeding 1.4 g/ml and preferably not exceeding 1.1 g/ml. In some embodiments of this invention agglomerates are at or close to neutral buoyancy or are light enough to float in the carrier liquid and do not settle.
[0021] The denser first particulate material may have greater strength to resist crushing than does the lighter second particulate material. When the fracture is allowed to close onto the particulate material, the agglomerates will be squeezed and eventually subjected to the crushing pressure of the rock formation. The second, lighter, particulate material may be crushed and deformed so that it does not function as a proppant, but this failure of the second material will be acceptable because the first material has been placed in the fracture and acts as the desired proppant. The overall result is an improvement in the effectiveness of a fracturing operation because the length of fracture which remains propped open is greater than would be the case if the first particulate material was used alone.
[0022] It is also possible that the lighter second particulate material has adequate strength to resist crushing but is more expensive than the first particulate material. In this event the use of both particulate materials gives an economic benefit: the second material assists transport and leads to the benefit that proppant is again carried further into the fracture then would be the case if the first, denser proppant was used alone, while but the use of a mixture of particulate materials is less expensive than using only the more expensive second material.
[0023] The first hydrophobic particles (which are the denser particulate material) may have a specific gravity of 1.8 or above, possibly at least 2.0 or 2.5, although it is also possible that the first particulate material could be a lightweight material such as material with specific gravity in a range from 1.5 or 1.6 up to 1.8. The second, lighter hydrophobic particulate material may have a specific gravity less than 1.5 and preferably less than 1.3. The second particulate material may possibly have a specific gravity not greater than 1.0. The amounts of the first and second particulate materials may be such that they have a ratio by volume in a range from 5:1 to 1:5, possibly 4:1 to 1:4 and possibly 3:1 to 1:4.
[0024] Sometimes a figure quoted in the literature for the density of a particulate material is a bulk density which is the mean density of a quantity of the particulate material together with anything present in the interstitial spaces between particles. On this basis, wet sand has a higher density than dry sand because the bulk density includes water between particles of sand. By contrast, specific gravity of the particulate materials refers to the specific gravity of the particles themselves, without considering interstitial material. For individual particles specific gravity is the weight of a particle relative to the weight of an equal volume of water. If the particles are formed of a homogenous material it is the specific gravity of that material. If the particles are hollow the specific gravity is still the weight of a particle relative to the weight of an equal volume of water, but this value of specific gravity is a value for the outer shell and the enclosed hollow interior together.
[0025] The first and second particles may be formed of materials which are inherently hydrophobic or may be particles which are hydrophilic but have a hydrophobic coating on their surface. For instance, ordinary silica sand which is commonly used as a proppant is hydrophilic and is not agglomerated by oil or gas in the presence of water. By contrast, we have found that sand which has been surface treated to make it more hydrophobic will spontaneously agglomerate in the presence of oil, air or nitrogen gas. The first particulate material used for this invention may be such hydrophobically modified sand. As an alternative to sand or other mineral, the particulate material could be a manufactured ceramic proppant, treated to give it a hydrophobically modified surface.
[0026] A quantitative indication of the surface polarity of a solid (prepared with a smooth, flat surface) is the concept of critical surface tension pioneered by Zisman (see Fox and Zisman J. Colloid Science Vol 5 (1950) pp 514-531 at page 529). It is a value of surface tension such that liquids having a surface tension against air which is lower than or equal to this value will spread on the surface of the solid whereas those of higher surface tension will remain as droplets on the surface, having a contact angle which is greater than zero. A strongly hydrophobic solid has a low critical surface tension. For instance the literature quotes a critical surface tension for polytetrafluoroethylene (PTFE) of 18.5 mN/m and for a solid coated with heptadecafluoro-1,1,2,2-tetra-hydro-decyl-trichlorosilane the literature value of critical surface tension is 12 mN/m. By contrast the literature values of critical surface tension for soda-lime glass and for silica are 47 and 78 mN/m respectively.
[0027] We have found that an analogous measurement of the hydrophobicity of the surface of a particulate solid can be made by shaking the solid with a very hydrophobic oil (preferably a silicone oil) having a low surface tension and mixtures of ethanol and water with a progressively increasing proportion of ethanol. This may be done at a room temperature of 20° C. The surface tensions of a number of ethanol and water mixtures are tabulated in CRC Handbook of Chemistry and Physics, 86 th edition, section 6 page 131.
[0028] Increasing the proportion of ethanol in the aqueous phase (i.e. the ethanol and water mixture) reduces its surface tension. Eventually a point is reached when the surface tension of the aqueous phase is so low that the solid can no longer be agglomerated by the oil. The boundary value at which agglomeration by the oil ceases to occur is a measure of the hydrophobicity of the solid and will be referred to as its “agglomeration limit surface tension” or ALST.
[0029] We have observed that particulate solids which can undergo spontaneous aggregation from suspension in deionised water on contact with oil always display an ALST value of approximately 40 mN/m or less. This ALST test covers a range of values of practical interest, but it should be appreciated that if no agglomeration takes place, this test does not give a numerical ALST value, but demonstrates that the surface does not have an ALST value of 40 mN/m or less. Moreover, if the surface has an ALST value below the surface tension of pure ethanol (22.4 mN/m at 20° C.), this test will not give a numerical ALST value but will show that the ALST value is not above 22.4 mN/m.
[0030] When particulate materials to be agglomerated are not inherently hydrophobic, a range of different methods can be used to modify the surface of solid particles to become more hydrophobic—these include the following, in which the first three methods provide covalent bonding of the coating to the substrate.
[0031] Organo-silanes can be used to attach hydrophobic organo-groups to hydroxyl-functionalized mineral substrates such as proppants composed of silica, silicates and alumino-silicates. The use of organosilanes with one or more functional groups (for example amino, epoxy, acyloxy, methoxy, ethoxy or chloro) to apply a hydrophobic organic layer to silica is well known. The reaction may be carried out in an organic solvent or in the vapour phase (see for example Duchet et al, Langmuir (1997) Vol 13 pp 2271-78).
[0032] Organo-titanates and organo-zirconates such as disclosed in U.S. Pat. No. 4,623,783 can also be used. The literature indicates that organo-titanates can be used to modify minerals without surface hydroxyl groups, which could extend the range of materials to undergo surface modification, for instance to include carbonates and sulphates.
[0033] A polycondensation process can be used to apply a polysiloxane coating containing organo-functionalised ligand groups of general formula P—(CH 2 ) 3 —X where P is a three-dimensional silica-like network and X is an organo-functional group. The process involves hydrolytic polycondensation of a tetraalkoxysilane Si(OR) 4 and a trialkoxysilane (RO) 3 Si(CH 2 ) 3 X. Such coatings have the advantage that they can be prepared with different molar ratios of Si(OR) 4 and (RO) 3 Si(CH 2 ) 3 X providing “tunable” control of the hydrophobicity of the treated surface.
[0034] A fluidized bed coating process can be used to apply a hydrophobic coating to a particulate solid substrate. The coating material would typically be applied as a solution in an organic solvent and the solvent then evaporated within the fluidized bed.
[0035] Adsorption methods can be used to attach a hydrophobic coating on a mineral substrate. A surfactant monolayer can be used to change the wettability of a mineral surface from water-wet to oil-wet. Hydrophobically modified polymers can also be attached by adsorption.
[0036] The surface modification processes above may be carried out as a separate chemical process before the wellbore fluid is formulated. Such pretreatment of solid material to make it hydrophobic would not necessarily be carried out at the well site; indeed it may be done at an industrial facility elsewhere and the pretreated material shipped to the well site. However, it is also possible that some of the above processes, especially an adsorption process, could be carried out at the well site as part of the mixing procedure in which the wellbore fluid is made.
[0037] Either or both of the particulate materials of this invention may be inherently hydrophobic but available hydrophobic materials tend to be lighter and thus more suitable as the second particulate material. Thus, one possibility within this invention is that the denser first particulate material is a solid mineral material such as sand with a hydrophobic coating on the exterior of the particles while the second, lighter, particles are an inherently hydrophobic material. Possible materials are natural or synthetic rubbers and hydrophobic polymers such as polyethylene and polypropylene. Polymers may be partially crosslinked or may contain strengthening fillers. For the sake of economy, hydrophobic materials may be materials which are being recycled after a previous use, for example comminuted recycled motor tyres or comminuted recycled polypropylene packaging. Other candidate materials are particles of coal or coal fractions.
[0038] Another possibility within this invention is that the second, lighter, particles are hollow. Glass microspheres with a hydrophobic coating are one possibility. We have found that such microspheres can remain intact under significant hydrostatic pressure, although they may later be crushed when a hydraulic fracture closes onto agglomerated proppant within it.
[0039] A range of glass microspheres (with a hydrophilic glass surface) are commercially available. Suppliers include 3M Inc and other manufacturers. Available microspheres have specific gravity ranging from 0.125 to 0.6 and the crush strength of such particles increases with their specific gravity. For example microspheres are available with a d 50 median particle size of 40 micron, a specific gravity of 0.38 and crush strength able to withstand pressures up to 4000 psi (27.58 MPa). Microspheres are also available with d 50 of 40 micron, a specific gravity of 0.6 and crush strength able to withstand pressures up to 10000 psi (68.95 MPa). Commercially available hydrophilic glass spheres can be made hydrophobic by a surface coating applied by one of the methods mentioned above.
[0040] A further possibility is that the second particulate material is a porous solid, such as volcanic pumice, with a hydrophobic coating. Such a material will have light weight because of the air filled pores: the aqueous carrier liquid will not invade these pores because of their small diameter and the hydrophobic coating.
[0041] Both particulate solids must of course form a separate solid phase when the agglomeration takes place. At this time they must therefore be insoluble in the carrier liquid, or at least be of low solubility. For many applications of this invention it will be desirable that the particulate solids remains insoluble after agglomeration has taken place. However, it is within the scope of some forms of this invention that the agglomerates might not have a permanent existence and might in time dissolve in surrounding liquid. For instance, incorporation of hydrophobically modified calcium carbonate within a mixed agglomerate with hm-silica would lead to agglomerates which could be partially dissolved by subsequent flow of an acidic solution able eventually to penetrate the hydrophobic coating.
[0042] The solid particles used in this invention may vary considerably in shape and size. They may have irregular shapes typical of sand grains which can be loosely described as “more spherical than elongate” where the aspect ratio between the longest dimension and the shortest dimension orthogonal to it might be 5 or less or even 2 or less. Other shapes such as cylinders or cubes are possible, notably if the particles are a manufactured ceramic product. A further possibility is that particulate material may have a platy form, as is the case with mica particles (indeed hydrophobically modified mica particles may be used as the first particulate material). In general, median particle sizes are unlikely to be larger than 5 mm. Median particle sizes are more likely to be 3 mm or less and preferably are 1.6 mm or less. Embodiments of this invention may use mixtures of solid particles where the median particle size is less than 1 mm. It is possible, especially for the denser first material, that at least 90% by volume of the particles have a longest dimension of less than 5 mm, possibly 3 mm or less.
[0043] Particle sizes may conveniently be specified by reference to sieve sizes, as is traditional for proppant materials. American Petroleum Institute Recommended Practices (API RP) standards 56 and 60 specify a number of proppant sizes by stating upper and lower US Sieve sizes. 90 wt % of a sample should pass the larger sieve but be retained on the smaller sieve. Thus ‘20/40 sand’ specifies sand having a particle size distribution such that 90 wt % of it passes 20 mesh (840 micron) but is retained on 40 mesh (420 micron). Correspondingly 90 wt % of a sample of 70/140 sand, which is the smallest size recognized by these standards, passes a 70 mesh (210 micron) sieve but is retained on a 140 mesh (105 micron) sieve. It will be appreciated that for any proppant specified by upper and lower sieve sizes, the median and mean particle sizes fall somewhere between the upper and lower sieve sizes.
[0044] Another method for determining size of particles is the commonly used technique of low angle laser light scattering, more commonly known as laser diffraction. Instruments for carrying out this technique are available from a number of suppliers including Malvern Instruments Ltd., Malvern, UK. The Malvern Mastersizer is a well known instrument which determines the volumes of individual particles, from which mean and median particle size can be calculated using computer software which accompanies the instrument. When determining particle sizes using such an instrument, the size of an individual particle is reported as the diameter of a spherical particle of the same volume, the so-called “equivalent sphere”. Volume median diameter denoted as D[v,05] or d 50 is a value of particle size such that 50% (by volume) of the particles have a volume larger than the volume of a sphere of diameter d 50 and 50% of the particles have a volume smaller than the volume of a sphere of diameter d 50 . Particle sizes determined by low angle laser light scattering are similar to particle sizes determined by sieving if the particles are approximately spherical.
[0045] Particle size distribution is then conveniently indicated by the values of d 10 and d 90 measured in the same way. 10% by volume of the particles in a sample have an equivalent diameter smaller than d 10 . 90% by volume are smaller than d 90 and so 10% by volume are larger than d 90 . The closer together the values of d 10 and d 90 , the narrower is the particle size distribution.
[0046] In forms of this invention where the first particulate material is a proppant for hydraulic fractures, the first particles may have a d 90 upper size similar to that of conventional proppant, such as 10 mesh (2 mm) or 20 mesh (840 microns). Their particle size properties may be such that
[0047] d 10 >110 micron, possibly >120 micron or >150 micron
[0048] d 50 <1 mm, possibly <800 micron
[0049] d 90 <3 mm, possibly <2 mm or <1 mm
[0050] The particle size distribution may be sufficiently wide that d 90 is more than 5 times d 10 , possibly more than 10 times d 10 . These particle size properties may also apply to other forms of this invention, such as those where the method of the invention is applied to preventing lost circulation, or achieving isolation of one zone from another.
[0051] However, it is an advantageous feature of this invention that it can be utilized with a first particulate material having a d 50 of 105 microns or less. We have found that use of a fine particulate material of this size may be advantageous for fracturing shale, notably for fracturing of a gas-bearing shale. Using a fine mesh proppant, that is to say a proppant of small particle size, may be expected to lead to fractures with lower permeability and conductivity than would be achieved with a proppant of larger size. Nevertheless, such fractures can carry gas with acceptable flow rates. The benefit of conveying proppant further into a fracture, so that the fracture has a greater effective size after it closes onto the proppant outweighs the lower conductivity. Overall, the stimulation of the formation is greater.
[0052] A fine mesh proppant may have d 90 below 150 microns, d 50 below 105 micron and d 10 of at least 10 microns. A possible material for use as a fine, first particulate material is hydrophobically modified flyash. So called flyash is recovered from the flue gas of coal fired power plants, and is a small particle size material with a high silica content. It typically has d 90 below 100 micron and specific gravity in the range 1.9 to 2.4.
[0053] The second particulate material used in this invention may or may not be of similar particle size to the first. One possibility is that the second particulate material is of somewhat smaller particle size than the first particulate material, especially if the first material has d 50 >120 microns. A candidate for a small size second particulate material is hydrophobically modified hollow spheres, where the hollow spheres (also termed cenospheres) are extracted from flyash. (Cenospheres which form spontaneously in the combustion process are a small percentage of flyash).
[0054] It is also possible that one or both of the particulate materials consists of, or includes, hydrophobic elongate fibres. Including fibres in the agglomerated solid may lead to agglomerates which are resistant to change in shape after agglomeration. For fibres, as for other particulate materials, it is preferred that the ALST value does not exceed 38 mN/m. An example of hydrophobic fibres which could be used alone or mixed with other particulate solid is polypropylene fibres having median diameter in a range from 50 to 500 micron and a median length of 3 to 10 mm. Another possibility would be glass fibres of these dimensions modified with a hydrophobic surface layer, suitably by one of the methods mentioned above.
[0055] In the context of hydraulic fracturing, it has been found useful to use a first particulate material which serves as a proppant and has a low aspect ratio together with a second, lighter, material which consists of, or includes, hydrophobic fibres. These fibres then reduce the density of the agglomerates during transport and also hinder the eventual settling of proppant from suspension by reason of their shape (which is the subject of another patent application filed concurrently with this application).
[0056] The agglomerating agent which binds the particles together as agglomerates is a gas. This gas must be sufficiently hydrophobic to form a phase which does not dissolve in the aqueous carrier liquid, although it is possible for it to have some limited water solubility, as is the case with air and with nitrogen. The volume of gas provided must be sufficient that it agglomerates the particles at downhole pressure. As pointed out above, however, the amount of gas required to bring about agglomeration will be less than if gas was the sole means to reduce the density of particulates.
[0057] As mentioned above the amount of gas which can be retained in agglomerates has an upper limit. We have found that agglomeration by gas may be assisted and improved if a small amount of hydrophobic oil is present. However, the amount should be small, such as not more than 10% or not more than 5% or even not more than 2% by volume of the amount of gas downhole. If the amount of oil is larger, agglomeration occurs but the oil displaces gas from the agglomerates and so the amount of gas which can be held by agglomerates is reduced.
[0058] The aqueous carrier liquid which is used to transport the particles may be a non-viscous or slickwater formulation. Such a formulation is typically water or a salt solution containing at least one polymer which acts as a friction reducer. A combination of polymers may be used for this purpose. Polymers which are frequently used and referred to as “polyacrylamide” are homopolymers or copolymers of acrylamide. Incorporation of a copolymer can serve to give the “modified” polyacrylamide some ionic character. A polyacrylamide may considered a copolymer if it contains more than 0.1% by weight of other comonomers. Mixtures of homopolymers and copolymers may be used. Copolymers may include two or more different comonomers and may be random or block copolymers. The comonomers may include, for example, sodium acrylate. The polyacrylamide polymers and copolymers useful as friction reducers may include those having an average molecular weight of from about 1000 up to about 20 million, or possibly above, with from about 1 million to about 5 million being typical. Other suitable friction reducers may be used as well; for example vinyl sulfonates included in poly(2-acrylamido-2-methyl-1-propanesulfonic acid) also referred to as polyAMPS.
[0059] The polyacrylamide may be used in the treatment fluid an amount of from about 0.001% to about 5% by weight of the treatment fluid but the amount is frequently not over 1% or even 0.5% by weight by weight. In many applications, the polyacrylamide is used in an amount of from about 0.01% to about 0.3% by weight of the fluid. The polyacrylamide may be initially dissolved or dispersed as a concentrate in mineral oil or other liquid carrier to enhance the delivery or mixability prior to its addition to water or a salt solution to make the carrier liquid.
[0060] A slickwater formulation may be substantially free of viscosity-enhancing polymeric thickener and have a viscosity which is not much greater than water, for instance not more than 15 centipoise, which is about 15 times the viscosity of water, when viscosity is measured at 20° C. and a shear rate of 100 sec −1 .
[0061] It is particularly envisaged that this invention will be used when fracturing a reservoir formation which has low permeability, so that slickwater is the fracturing fluid of choice. As mentioned above, this has considerable advantage when pumping into the formation but makes suspension of proppant much more difficult.
[0062] A reservoir formation of low permeability may well be a gas reservoir, although this is not inevitably so. It may be a gas-bearing shale. A formation of low permeability may have a permeability of no more than 10 millidarcies (10 mD), possibly no more than 1 millidarcy. Its permeability may be even lower, such as less than 100 microdarcy, or even less than 1 microdarcy.
[0063] This invention may also be used where the carrier liquid is a more traditional fracturing fluid incorporating a thickening agent to increase the viscosity of the fluid. Such a thickening agent may be a polymer. It may be a polysaccharide such as guar, xanthan or diutan or a chemically modified polysaccharide derivative such as hydroxyalkylcellulose or a hydroxyalkylguar. These polysaccharide thickeners may be used without cross linking or may be cross-linked to raise viscosity further. Viscoelastic surfactants are another possible thickening agent which may be used to increase viscosity. We have observed that some thickening of the carrier liquid does not prevent agglomeration, although it may be preferred that the viscosity is not allowed to become too high before agglomeration takes place.
[0064] The agglomeration of proppant particles will lead to some small-scale non-uniformity of the distribution of proppant within a fracture when the fracture is allowed to close onto the proppant. Distributing proppant throughout a fracture, but with some non-uniformity in the distribution of proppant (sometimes referred to as heterogeneous proppant placement) may be helpful in enhancing fracture conductivity. In some embodiments of this invention, localized non-unity may be deliberately enhanced.
[0065] One known method for heterogenous proppant placement which may be used in this invention is to pump a fluid containing suspended proppant alternately with a fluid containing less of the suspended proppant or none at all. This approach is the subject of U.S. Pat. No. 6,776,235. Another known method which may be employed is to pump the proppant together with a removable material, referred to as a ‘channelant’. After pumping has ceased and the fracture has closed onto proppant in the fracture, removal of the channelant leaves open pathways between islands or pillars of the proppant. This approach is the subject of WO2008/068645, the disclosure of which is incorporated herein by reference.
[0066] A degradable channelant material may be selected from substituted and unsubstituted lactide, glycolide, polylactic acid, polyglycolic acid, copolymers of polylactic acid and polyglycolic acid, copolymers of glycolic acid with other hydroxy-, carboxylic acid-, or hydroxycarboxylic acid-containing moieties, copolymers of lactic acid with other hydroxy-, carboxylic acid-, or hydroxycarboxylic acid-containing moieties, and mixtures of such materials. Representative examples are polyglycolic acid or PGA, and polylactic acid or PLA. These materials function as solid-acid precursors, and undergo hydrolytic degradation in the fracture.
[0067] Agglomerates of hydrophobic particles and a gas as agglomerating agent will form spontaneously in an aqueous carrier liquid when the materials are mixed together. One possibility is that the particulate materials, carrier liquid and agglomerating gas are all mixed together at the surface and then pumped down a wellbore. In this case the particles may agglomerate before passing through the pumps. If so, they may be sheared apart by the pumps, but spontaneously reform downstream from the pumps as they pass down the wellbore.
[0068] A possibility to avoid passing the agglomerates through the pumps is that the gas is compressed at the surface and then admitted to the high pressure flowline downstream of the surface pumps which are driving the carrier liquid and the particulate materials into the wellbore. As a variant of this, the gas could be transported down the wellbore in a separate pipe so as to travel to a considerable depth underground before mixing with the particulate materials.
[0069] Another approach is to allow the materials to mix, but inhibit agglomeration for at least part of the journey of the carrier liquid and entrained materials to the subterranean location where the agglomerates are required. Some possibilities for this are as follows:
[0070] Encapsulation or coating. The particulate materials are coated with a hydrophilic material which dissolves slowly or undergoes chemical degradation under conditions encountered at the subterranean location, thereby exposing the hydrophobic surface within. Degradation may in particular be hydrolysis which de-polymerises an encapsulating polymer. While such hydrolytic degradation may commence before the overall composition has travelled down the wellbore to the reservoir, it will provide a delay before contact between agglomerating gas and exposed hydrophobic surface becomes significant.
[0071] A number of technologies are known for the encapsulation of one material within another material. Polymeric materials have frequently been used as the encapsulating material. Some examples of documents which describe encapsulation procedures are U.S. Pat. No. 4,986,354, WO 93/22537 and WO 03/106809. Encapsulation can lead to particles in which the encapsulated substance is distributed as a plurality of small islands surrounded by a continuous matrix of the encapsulating material. Alternatively encapsulation can lead to core-shell type particles in which a core of the encapsulated substance is enclosed within a shell of the encapsulating material. Both core-shell and islands-in-matrix type encapsulation may be used.
[0072] An encapsulating organic polymer which undergoes chemical degradation may have a polymer chain which incorporates chemical bonds which are labile to reaction, especially hydrolysis, leading to cleavage of the polymer chain. A number of chemical groups have been proposed as providing bonds which can be broken, including ester, acetal and amide groups. Cleavable groups which are particularly envisaged are ester and amide groups both of which provide bonds which can be broken by a hydrolysis reaction.
[0073] Generally, their rate of cleavage in aqueous solution is dependent upon the pH of the solution and its temperature. The hydrolysis rate of an ester group is faster under acid or alkaline conditions than neutral conditions. For an amide group, the decomposition rate is at a maximum under low pH (acidic) conditions. Low pH, that is to say acidic, conditions can also be used to cleave acetal groups.
[0074] Thus, choice of encapsulating polymer in relation to the pH which will be encountered after the particles have been placed at intended subterranean location may provide a control over the delay before the encapsulated material is released. Polymers which are envisaged for use in encapsulation include polymers of hydroxyacids, such as polylactic acid and polyglycolic acid. Hydrolysis liberates carboxylic acid groups, making the composition more acidic. This lowers the pH which in turn accelerates the rate of hydrolysis. Thus the hydrolytic degradation of these polymers begins somewhat slowly but then accelerates towards completion and release of the encapsulated material. Another possibility is that a polymer containing hydrolytically cleavable bonds may be a block copolymer with the blocks joined through ester or amide bonds.
[0075] Sensitivity to temperature. A development of the use of a hydrophilic coating makes use of the difference between surface temperatures and temperatures below ground, which are almost always higher than at the surface. During transit to the subterranean location, the carrier liquid and everything suspended in it will pass through a wellbore exposed to subterranean temperatures and will begin to heat up, but if the flow rate is substantial, the flowing composition will reach the subterranean location at a temperature well below the natural temperature at that location. In particular, in the case of hydraulic fracturing the fracturing fluid will leave the wellbore and enter the fracture at a temperature significantly below the reservoir temperature. A possibility, therefore, would be to coat the hydrophobic particles with a coating of a hydrophilic material which remains intact at surface temperatures, but melts or dissolves in the carrier liquid at the temperature encountered below ground.
[0076] Generating gas below ground. Another possible approach for delaying agglomeration during at least part of the journey of the materials to the subterranean location where the agglomerates are required is to generate the agglomerating gas chemically, for example by including aluminium powder in the composition and formulating the carrier liquid to be alkaline so that hydrogen is generated by reaction of aluminium and the aqueous alkaline carrier liquid. Conversely, iron or zinc particles could be incorporated in a fluid with pH below 7 to generate hydrogen. A further possibility for generating gas below ground would be to pump a neutral slickwater fluid containing suspended calcium carbonate particles, followed by an acidic slickwater fluid containing hydrophobic fibres and hydrophobic particulate proppant. Carbon dioxide would then be liberated below ground on contact between the acidic slickwater and the carbonate previously placed below ground. In the methods above for generating gas below ground, the solid material could be encapsulated in or coated with a material which dissolves or melts at the reservoir temperature, thus delaying the start of the chemical generation of gas. Another way to generate carbon dioxide would be to incorporate nanoparticulate polycarbonates which decompose, liberating carbon dioxide, at a temperature of around 150° C.
[0077] Discussion above has focused on placing particulate material below ground. However, the invention also has application to the removal of particulate material in wellbore clean-out. After hydrophobic particulate materials have been placed in a fracture (or other location underground) the removal of hydrophobic particulate material remaining in the wellbore can be carried out by using coiled tubing to pump gas, or a mixture of gas and aqueous liquid, into the bottom of the wellbore while the wellbore contains aqueous liquid. This gas will rise towards the surface. If it encounters hydrophobic particulate material it will agglomerate that material into lightweight particles which will rise or be carried upward to the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0078] FIG. 1 diagrammatically illustrates features of a close-packed agglomerate;
[0079] FIG. 2 similarly illustrates features of an agglomerate which is not close packed;
[0080] FIG. 3 is a graph of density against composition for mixtures of nitrogen and hydrophobically modified sand;
[0081] FIG. 4 diagrammatically illustrates an agglomerate of mixed particles;
[0082] FIG. 5 schematically illustrates the use of the invention in fracturing; and
[0083] FIG. 6 illustrates fracturing from a horizontal wellbore.
DETAILED DESCRIPTION
[0084] FIG. 1 diagrammatically illustrates a portion of an agglomerate formed from particles in a close packed arrangement. In this illustration the particles are spheres 10 of uniform size. The interstitial volume, that is the spaces 12 between particles, is determined by the geometry of the arrangement. For an agglomerate of a large number of close packed spheres of uniform size, it can be calculated that the interstitial volume amounts to a volume fraction of 0.36 while the spheres occupy a volume fraction of 0.64. If the particles are not spherical or are not uniformly sized the interstitial volume will be a different fraction of the overall volume, although still dependent on geometry. Notably, a mixture of particle sizes can give a closely packed arrangement in which the interstitial volume fraction is smaller than 0.36.
[0085] It can be envisaged that if the amount of agglomerating agent is larger than the interstitial volume of a close packed arrangement, the particles would still be agglomerated but will not be in a completely close packed state. They would instead be slightly spaced as shown in FIG. 2 and the interstitial volume would then be larger, thus taking up the available amount of agglomerating agent.
[0086] We have found that when hydrophobic particles are agglomerated with oil this does indeed happen. A quantity of oil in excess of the minimum amount required to bring about agglomeration can be included in the agglomerates. However, we have found that this does not happen, or does not happen to the same extent, when the agglomerating agent is gas.
[0087] FIG. 3 is a graph of density against volume fraction of nitrogen in hypothetical mixtures of hydrophobically modified sand (specific gravity 2.65) and nitrogen gas as an agglomerating agent. The specific gravity of the nitrogen gas is taken to be 0.081 at a pressure of 10 MPa and a temperature of 400° Kelvin (127° C.) representative of a downhole pressure and temperature. If the agglomerates were to have a nitrogen volume fraction of 0.64 (that is 64 parts by volume nitrogen and 36 parts by volume sand) they would have a density of 1 gm per ml, which is neutral buoyancy in water. However, we have found by experiment that stable agglomerates with air or nitrogen as agglomerating agent do not contain such a high volume of fraction of the gas and are denser than water, as will be shown in Example 5 below.
[0088] By contrast, if a mixture of denser and lighter hydrophobic particulate materials is used in accordance with this invention, a smaller volume fraction of gas is needed to achieve neutral buoyancy in water. The particles in such an agglomerate do not need to be the same size. FIG. 4 diagrammatically illustrates part of an agglomerate of first, denser particles 10 and second, less dense particles 11 , where the second particles 11 are smaller than the first particles 10 .
[0089] The table below sets out some calculated densities for agglomerates containing hydrophobically modified sand mixed with polypropylene particles having a specific gravity of 0.9. Again the agglomerating agent is nitrogen gas.
[0000] Volume fraction Density Composition of particulate mixture of nitrogen (g/ml) 80 vol % hm-sand 20 vol % polypropylene 0.36 1.5 60 vol % hm-sand 40 vol % polypropylene 0.36 1.28 40 vol % hm-sand 60 vol % polypropylene 0.36 1.05 35 vol % hm sand 65 vol % polypropylene 0.36 1.0 80 vol % hm-sand 20 vol % polypropylene 0.5 1.19 58 vol % hm sand 42 vol % polypropylene 0.5 1.0
It is apparent that neutral buoyancy, that is a density of 1 gm/ml, can be achieved with a smaller volume fraction of nitrogen if polypropylene particles are included.
[0090] Similar calculations were carried out for particulate mixtures containing hydrophobically modified sand and hydrophobically modified glass microspheres having specific gravity 0.6. The following combinations of materials and proportions were calculated to give agglomerates of neutral buoyancy (assuming that such agglomerates could be made and would be stable).
[0000]
Volume
fraction
Composition of particulate mixture
of nitrogen
Density
60 vol % hm-sand
40 vol % hm-microspheres
0.36
1.20
45 vol % hm-sand
55 vol % hm-microspheres
0.36
1.0
80 vol % hm sand
20 vol % hm-microspheres
0.5
1.16
65 vol % hm sand
35 vol % hm-microspheres
0.5
1.0
[0091] Even a second particulate material which is denser than water will reduce the amount of gas required to achieve neutral buoyancy. A mixture of 38 vol % hydrophobically modified sand and 62 vol % waste rubber having a specific gravity of 1.2 would require nitrogen in a volume fraction of 0.45 to achieve a density of 1 gm/ml, whereas sand alone would require a nitrogen volume fraction of 0.64.
[0092] In the following examples, Examples 1 to 4 illustrate the preparation of hydrophobically modified materials. Examples 5 onwards show the effect of using mixtures of hydrophobic particulate materials, in accordance with this invention.
Example 1
Hydrophobic Modification of Sand
[0093] Sand, having particle size between 20 and 40 US mesh (840 micron and 400 micron), i.e. 20/40 sand, was washed by mixing with ethanol at ambient temperature, then filtering, washing with deionised water and drying overnight at 80° C.
[0094] Quantities of this pre-washed sand were hydrophobically modified by treatment with various reactive organosilanes, using the following procedure. 75 gm pre-washed sand was added to a mixture of 200 ml toluene, 4 ml organo-silane and 2 ml triethylamine in 500 ml round bottomed flask. The mixture was refluxed under a nitrogen atmosphere for 4 to 6 hours. After cooling, the hydrophobically modified sand (hm-sand) was filtered off (on a Whatman glass microfiber GF-A filter) and then washed, first with 200 ml toluene, then 200 ml ethanol and then 800 ml deionised water. The hm-sand was then dried overnight at 80° C.
[0095] The above procedure was carried out using each of the following four reactive organo-silanes:
[0096] 5.64 gm Heptadecafluoro-1,1,2,2-tetrahydro-decyl-triethoxysilane (>95% purity, specific gravity=1.41 gm/ml).
[0097] 5.40 gm Tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane (>95% purity, specific gravity=1.35 gm/ml).
[0098] 3.53 gm Octadecyl-trimethoxysilane (90% purity, specific gravity=0.883 gm/ml).
[0099] 5.93 gm Octadecyldimethyl 3-trimethoxysilylpropyl ammonium chloride (60% active solution in methanol, specific gravity=0.89 gm/ml).
[0100] For convenience the hydrophobic groups introduced by these materials will be referred to hereafter as C 10 F 17 H 4 -silyl, C 8 F 13 H 4 silyl, C 18 H 37 -silyl and C 18 H 37 -aminopropylsilyl, respectively.
[0101] It was appreciated that these quantities of organo-silane were far in excess of the stoichiometric amount required to react with all the hydroxyl groups on the surface of the sand particles. 20/40 sand has specific surface area 0.0092 m 2 /gm (calculated from particle size distribution determined by laser diffraction (Malvern Mastersizer) method). The theoretical maximum concentration of hydroxyl (—OH) groups per unit area of silica surface, is 4.5 hydroxyl groups per square nanometre. From these values it can be calculated that 75 gm sand has (at most) 3.1×10 18 hydroxyl groups exposed on its surface. Using Avogadro's number, 5.64 gm (0.00924 mol) heptadecafluoro-1,1,2,2-tetra-hydro-decyl-triethoxysilane contains 5.56×10 21 molecules. Therefore there is a very high ratio of organo-silane molecules in the reaction solution to surface hydroxyl groups. The calculated number ratio in the case of the C 10 F 17 H 4 -silyl example above was organo-silane (solution) /OH (surface) =1792. It should be noted that at least some excess organosilane is removed from the treated sand during the filtration and washing stages.
Example 2
[0102] The procedure above was carried out with the following reduced quantities of organo-silane:
[0103] 0.27 gm Heptadecafluoro-1,1,2,2-tetra-hydro-decyl-triethoxysilane
[0000] number ratio organo-silane (solution) /OH (surface) =85.8.
[0104] 0.02 gm Heptadecafluoro-1,1,2,2-tetra-hydro-decyl-triethoxysilane
[0000] number ratio organo-silane (solution) /OH (surface) =6.4.
[0000] It was found the smallest amount of organo-silane was insufficient to render the sand adequately hydrophobic to be agglomerated.
Example 3
Condensation Coating
[0105] Pre-washed 20/40 sand, prewashed as in Example 1 above, was given a hydrophobic surface coating by the simultaneous condensation polymerization of tetraethylorthosilicate (TEOS) and tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane in 3:1 molar ratio under basic conditions.
[0106] 200 gm pre-washed sand, 12 ml of aqueous ammonia (NH 4 OH, 28%), 57 ml of absolute ethanol and 3 ml deionized water were mixed and stirred vigorously (Heidolph mechanical stirrer at 300-400 RPM) for 30 min. Then 0.73 gm (3.53 mmol) of TEOS and 0.6 gm (1.17 mmol) tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane were added and stirred for 3.5 hrs at room temperature. The resulting hm-sand was then filtered off, washed with ethanol and then with deionized water and dried at 120° C. overnight. This procedure was also carried out using pre-washed 70/140 sand with a mixture of tetraethylorthosilicate (TEOS) and heptadecafluoro-1,1,2,2-tetra-hydro-decyl-triethoxysilane.
Example 4
Condensation Coating of Glass Microspheres
[0107] The glass microspheres used had a mean diameter d 50 of 40 micron and a specific gravity of 0.6. 20 gm microspheres, 12 ml of aqueous ammonia (NH 4 OH, 28%), 57 ml of absolute ethanol and 3 ml deionized water were mixed and stirred vigorously (Heidolph mechanical stirrer at 300-400 RPM) for 30 min. Then 0.73 gm (3.53 mmol) of TEOS and 0.6 gm (1.17 mmol) tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane were added and stirred for 4 hrs at room temperature. The resulting hm-microspheres were then filtered off, washed with ethanol and then with deionized water and dried at 120° C. overnight.
Example 5
Agglomeration of hm-Sand and Polypropylene
[0108] Sample mixtures were prepared using 20/40 sand, hydrophobically modified with tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane as in Example 3 and varying proportions of 20/40 polypropylene particles, having a specific gravity of 0.9. The amounts are given in the following table:
[0000]
Sample
C 8 F 13 H 4 -
Polypropylene
Volume fraction
number
sand 20/40
20/40
polypropylene
1
2 g
none
0
2
2 g
0.2 g
0.23
3
2 g
0.4 g
0.37
4
2 g
0.6 g
0.47
5
2 g
1.0 g
0.6
[0109] Each sample was mixed with 16 ml of deionised water in a bottle of about 30 ml capacity, thus leaving an air-filled headspace of about 10-15 ml in the bottle. The bottle was closed and shaken vigorously so that the solids could be agglomerated with air from the headspace.
[0110] In the case of the first sample, without polypropylene, a single agglomerate with a smoothly curved surface was formed. This demonstrated that hydrophobically modified 20/40 sand could be agglomerated with air. However, the agglomerate sank to the bottom of the bottle and no change was achieved through further shaking. Since the amount of air in the headspace was larger than the agglomerate formed, it was apparent that the amount of air in the agglomerate had reached the maximum which the agglomerate could retain, indicating that the amount of air which could be retained in the agglomerate was not a sufficiently large volume fraction to give an agglomerate of neutral buoyancy.
[0111] In the case of samples 2 and 3 with 0.2 g or 0.4 g polypropylene present the agglomerates again sank to the bottom of the bottle but were less firmly settled than the agglomerate without polypropylene, indicating that the polypropylene in the agglomerates together with the in them was reducing the density compared with the agglomerate without polypropylene. With 0.6 g or 1 g polypropylene present reduction of density went further and some of the agglomerates floated to the top of the water in the bottles.
[0112] Next nitrogen was bubbled into the bottles near the bottom of each one. Nearly all of the agglomerates formed from sample 4 with 0.6 g polypropylene present floated in the water. In the case of sample 5 with 1.0 g polypropylene present, all the agglomerates floated in the water.
[0113] This experiment was repeated with the modification that five drops of dodecane were added to the samples before nitrogen was bubbled into the bottom of each bottle. Yet again the sample without polypropylene formed a single agglomerate which sank. The agglomerates from samples 4 and 5, with 0.6 g and 1 g polypropylene present all floated. This indicates that a small amount of oil, occupying only a small volume fraction, increases the efficacy of gas in reducing the density of agglomerates.
Example 6
[0114] The previous example was repeated using the same, hydrophobically modified 20/40 sand but smaller polypropylene particles all of which passed a 40 mesh sieve. After shaking the closed bottles where some polypropylene was present, slightly more of the agglomerates floated than in the previous example. After bubbling in nitrogen, for the samples with 0.4 g, 0.6 g and 1.0 g polypropylene present, all the agglomerates floated at the top of the water in the bottles. This indicates that the smaller polypropylene particles assisted the reduction in density of the agglomerates formed.
Example 7
Agglomeration of hm-Sand and hm-Microspheres
[0115] Samples were prepared using varying proportions of 20/40 sand, hydrophobically modified with tridecafluoro-1,1,2,2-tetrahydro-octyl-triethoxysilane as in Example 3 and hydrophobically modified glass microspheres prepared as in Example 4. The amounts are given in the following table:
[0000]
20/40 hm-sand
hm-microspheres
Sample
Wt
Vol
Wt
Vol
Total vol.
Vol %
No.
(g)
(ml)
(g)
(ml)
solids (ml)
microspheres
1
2
0.755
0
0
0.755
2
1.5
0.566
0.113
0.189
0.755
25
3
1.0
0.377
0.226
0.377
0.754
50
4
0.5
0.189
0.340
0.566
0.755
75
[0116] Each sample was mixed with 20 ml of deionised water in a bottle of about 30 ml capacity, thus leaving an air-filled headspace in the bottle of 10 ml or more. The bottle was closed and shaken vigorously so that the solids could be agglomerated with air from the headspace.
[0117] In the case of the sample 1, without microspheres, a single agglomerate was formed, just as with sample 1 of Example 5. For all samples with microspheres present some agglomerates sank to the bottom of the bottle but were less firmly settled than the agglomerate without microspheres and some agglomerates floated to the top of the water in the bottles.
[0118] Next nitrogen was bubbled into the bottles near the bottom of each one. Almost all of the agglomerates formed from sample 4 with 75 vol % microspheres floated in the water. In the case of sample 5 with 1.0 g polypropylene present, all the agglomerates floated in the water.
[0119] This experiment was repeated with the modification that five drops of dodecane were added to the samples before nitrogen was bubbled into the bottom of each bottle. Yet again the sample without microspheres formed a single agglomerate which sank. The agglomerates from samples 3 and 4, with 50 vol % and 75 vol % microspheres, all floated. This indicates that a small amount of oil, occupying only a small volume fraction, increases the efficacy of gas in reducing the density of agglomerates.
Example 8
[0120] A procedure similar to the previous example was carried out, replacing the 20/40 sand with 70/140 sand, hydrophobically modified with heptadecafluoro-1,1,2,2-tetrahydro-decyl-triethoxysilane as in Example 3. The amounts of materials were as set out in the following table:
[0000]
20/40 hm-sand
hm-microspheres
Sample
Wt
Vol
Wt
Vol
Total vol.
Vol %
No.
(g)
(ml)
(g)
(ml)
Solids (ml)
microspheres
1
2
0.755
0
0
0.755
2
1.5
0.566
0.113
0.189
0.755
25
3
1.0
0.377
0.226
0.378
0.755
50
[0121] Each sample was mixed with 20 ml of deionised water in a bottle of about 30 ml capacity, thus leaving an air-filled headspace in the bottle of 10 ml or more. The bottle was closed and shaken vigorously so that the solids could be agglomerated with air from the headspace. As before, in the absence of glass microspheres the hm-sand forms an agglomerate which sinks in water. With 25 vol % microspheres, some agglomerates floated (a larger proportion than with 20/40 hm sand in the previous example) and with 50% microspheres almost all agglomerates floated.
[0122] A similar result was observed when nitrogen was bubbled into each bottle. The experiment was repeated with the modification that five drops of dodecane were added to the samples before nitrogen was bubbled into the bottom of each bottle. Yet again the sample without microspheres formed a single agglomerate which sank. With 25 vol % microspheres and again with 50 vol % microspheres all the agglomerates floated. This again indicates that a small amount of oil, occupying only a small volume fraction, increases the efficacy of gas in reducing the density of agglomerates.
[0123] As a control experiment, 0.5 g 70/14 hm-sand was mixed with 0.34 g of unmodified glass microspheres and 20 g deionised water. This quantity of microspheres amounts to 74 vol % of the solids. On shaking with air the unmodified glass microspheres did not agglomerate and floated at the surface of the water. The hm-sand formed an air agglomerate which sank to the base of the bottle.
Application of the Invention
[0124] To illustrate and exemplify use of some embodiments of the method of this invention, FIG. 5 shows diagrammatically the arrangement when a fracturing job is carried out. A mixer 14 is supplied with a small amount of viscosity reducing polymer, a small amount of oil, first and second particulate materials and water as indicated by arrows V, O P 1 , P 2 , and W. The mixer delivers a mixture of these materials to pumps 16 which pump the mixture under pressure down the production tubing 18 of a wellbore 20 . Nitrogen from a supply 22 pressurized by compressor 24 is driven down a tube 26 within the production tubing 18 and forms agglomerates of the particulate materials when it exits into the flow within tubing 18 . The aqueous carrier liquid and suspended agglomerates 28 then pass through perforations 30 into the reservoir formation 32 as indicated by the arrows 34 at the foot of the well.
[0125] In the early stages of the fracturing job, the fluid does not contain particulate solid nor added nitrogen but its pressure is sufficiently great to initiate a fracture 36 in the formation 32 . Subsequently the particulate materials and nitrogen are mixed, as described above, with the fluid which is being pumped in. Its pressure is sufficient to propagate the fracture 36 and as it does so it carries the suspended agglomerates 28 into the fracture 36 . Because the agglomerates have a low density they do not settle out at the entrance to the fracture, but are carried deep into the fracture.
[0126] FIG. 6 illustrates the use of tubing 40 , which may be coiled tubing, to form fractures within a horizontal wellbore. As illustrated here, fracture 42 has already been formed and has been closed off by a temporary plug 44 . Fracture 46 is being formed. In a manner generally similar to the arrangement of FIG. 5 , water, friction reducing polymer, a small quantity of oil and the mixed particulate materials are supplied under pressure through tubing 40 . Pressurized nitrogen is supplied along smaller tubing 48 . Agglomerates form as nitrogen gas exits from the tubing 48 , and the flow of carrier liquid delivers these into the fracture 46 which extends both upwards and downwards from the wellbore.
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A wellbore fluid is an aqueous carrier liquid with first and second hydrophobic particulate materials suspended therein. The first hydrophobic particles have a higher specific gravity than the second hydrophobic particles and the fluid also comprises a gas to wet the surface of the particles and bind them together as agglomerates. The fluid may be a fracturing fluid or gravel packing fluid and the first particulate material may be proppant or gravel. The lighter second particulate material and the gas both reduce the density of the agglomerates which form so that they settle more slowly from the fluid, or are buoyant and do not settle. This facilitates transport and placement in a hydraulic fracture or gravel pack. One application of this is when fracturing a gas-shale with slickwater. The benefit of reduced settling is better placement of proppant so that a greater amount of the fracture is propped open.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to a certain polymorphic form and pharmaceutical science.
BACKGROUND OF THE INVENTION
[0002] Polymorphism relates to the occurrence of different crystal forms for a molecule. These different crystalline forms have distinct crystal structures and vary in physical properties like melting point and XRPD spectrum. A particular polymorph may have advantageous properties for the manufacture and use of the drug substance.
[0003] The present invention relates to a particular polymorphic form of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, free base, which is an antagonist of the 5-HT3 receptor. 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, 2,2,2-trifluoroacetic acid salt, is disclosed in PCT Publication No. WO 2014/014951, published Jan. 23, 2014.
[0004] The present polymorphic form, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, provides an anhydrate form, that can be readily and reproducibly produced and is stable to prolonged thermal stress.
SUMMARY OF THE INVENTION
[0005] The present invention provides a novel polymorph of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide. More specifically, the present invention provides 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G.
[0006] The present invention also provides a pharmaceutical composition comprising 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, and a pharmaceutically acceptable excipient.
[0007] The present invention also provides a methods of treating a disease treatable by administration of a 5-HT3 receptor antagonist which method comprises administrating to the patient 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. That is, the present invention provides a method of treating a disease treatable by administration of a 5-HT3 receptor antagonist comprising: administrating to a patient in need thereof a therapeutically effective amount of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. The invention is directed to the use of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, to treat a disease treatable by administration of a 5-HT3 receptor antagonist as disclosed herein, that is, the use of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, for the manufacture of a medicament to treat diseases treatable by administration of a 5-HT3 receptor antagonist as disclosed herein.
BRIEF DESCRIPTION OF THE DRAWING
[0008] The drawing shows X-ray powder diffraction patterns (counts vs. degrees 2-theta) of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, which was prepared from a hydrate of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide using different solvents and/or conditions for crystallization: (a) starting material heated to 50° C. in DMSO, followed by aqueous NaOH (4 M); mixture stirred at 50° C. for 30 minutes and then allowed to cool to room temperature over a 4-hour period; (b) starting material heated to 70° C. in MeCN, followed by addition of H 2 O at 70° C.; mixture placed in a refrigerator at 4° C. for 16 hours; (c) starting material heated to 70° C. in DMSO, followed by addition of H 2 O at 70° C.; mixture placed in a refrigerator at 4° C. for 16 hours; (d) starting material heated to 70° C. in NMP, followed by addition of H 2 O at 70° C.; mixture placed in a refrigerator at 4° C. for 16 hours; (e) starting material heated to 70° C. in DMSO, followed by addition of H 2 O at 70° C.; mixture cooled at 20° C./hour to room temperature and allowed to equilibrate at room temperature over a 16-hour period.
DETAILED DESCRIPTION OF THE INVENTION
[0009] As used herein terms have their using conventional abbreviations, unless otherwise indicated, for example: methanol (MeOH), ethanol (EtOH), isopropanol (IPA), n-butanol (n-BuOH), acetonitrile (MeCN), tetrahydrofuran (THF), 2-methyl tetrahydrofuran (2-MeTHF), MeOAc (methyl acetate), ethyl acetate (EtOAc), isopropyl acetate (IPAc), methyl ethyl ketone (MEK), methylisobutyl ketone (MIBK), dichloromethane (DCM), dimethyl sulfoxide (DMSO), dimethylamide (DMF), and N-methyl-2-pyrrolidone (NMP).
[0010] As used herein, the term “C 2-4 alkylnitrile” refers to a straight or branched alkyl chain having a nitrile, and having a total of from two to four carbon atoms, for example acetonitrile and propionitrile.
[0011] The term “C 3-7 alkylacetate” refers to straight or branched alkyl esters of acetic acid having a total of three to seven carbons, for example, ethyl acetate, isopropyl acetate, and the like.
[0012] The term “C 1-6 alcohol” a straight or branched alcohols having from one to six carbon atoms, for example methanol, ethanol, n-propanol, iso-propanol, 1,3-propanediol, and the like.
[0013] The term “C 2-8 ether” refers to a straight, branched, or cyclic alkyl ethers having a total of from two to eight carbon atoms, for example diethyl ether, methyl-t-butyl ether, THF, dioxane, and the like.
[0014] The term “C 6-9 aromatic hydrocarbons” refers to benzene and alkyl substituted benzene, such a toluene, xylene, and the like.
[0015] The term “C 3-5 N,N-dimethylcarboxamides” refers to N,N-dimethylamides of a C 1-3 carboxylic acid, for example N,N-dimethylformamide.
[0016] The term “C 3-7 alkanones” refers to a straight or branched alkyl chain having an oxo group and having a total of from three to seven carbon atoms, for example acetone and methyl ethyl ketone.
[0017] It is understood that the terms “crystallize,” “crystallizing,’ and “crystallization” include complete dissolution followed by precipitation and slurry processes that do not involve complete dissolution.
[0018] A “pharmaceutically acceptable carrier or excipient” means a carrier or an excipient that is useful in preparing a pharmaceutical composition that is generally safe, non-toxic and neither biologically nor otherwise undesirable, and includes a carrier or an excipient that is acceptable for veterinary use as well as human pharmaceutical use. The term “pharmaceutically acceptable excipient” as used in the specification and claims includes both one and more than one such excipient. Pharmaceutically acceptable excipients are well known in the art, such as those in Remington's Pharmaceutical Sciences, 17th ed., Mack Publishing Company, Easton, Pa., 1985.
[0019] The terms “condition,” “disorder,” and “disease” relate to any unhealthy or abnormal state.
[0020] “Treat,” “treating,” or “treatment” of a disease includes:
[0021] (1) preventing the disease, i.e. causing the clinical symptoms of the disease not to develop in a mammal that may be exposed to or predisposed to the disease but does not yet experience or display symptoms of the disease;
[0022] (2) inhibiting the disease, i.e., arresting, controlling, slowing, stopping, or reducing the development of the disease or its clinical symptoms; or
[0023] (3) relieving the disease, i.e., causing regression of the disease or its clinical symptoms or improvement of the disease or its clinical symptoms. The terms “treat,” “treating,” and “treatment,” do not necessarily indicate a total elimination of any or all symptoms or a cure of the disease.
[0024] As used herein the terms “patient” and “subject” includes humans and non-human animals, for example, mammals, such as mice, rats, guinea pigs, dogs, cats, rabbits, cows, horses, sheep, goats, and pigs. The term also includes birds, fish, reptiles, amphibians, and the like. It is understood that a more particular patient is a human. Also, more particular patients and subjects are non-human mammals, such as mice, rats, and dogs.
[0025] The term “substantially pure” refers to greater than 90%, preferably greater than 97%, and more preferably greater than 99% polymorphic purity.
[0026] A “therapeutically effective amount” means the amount of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, that when administered in single or multiple doses, to a mammal for treating a disease, is sufficient to effect such treatment for the disease. The “therapeutically effective amount” can vary depending on the disease and its severity; the age, weight, etc., of the mammal to be treated; the degree of or involvement or the severity of the condition, disorder, or disease; the response of the individual patient; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances.
[0027] The term “disease treatable by administration of a 5-HT3 receptor antagonist” includes emesis, migraine, substance abuse and addiction, neurodegenerative and psychiatric disorders such as anxiety and depression, eating disorders, schizophrenia, cognitive dysfunction associated with schizophrenia, Parkinson's disease, Huntington's Chorea, presenile dementias and Alzheimer's disease, and pain; GI disorders such as dyspepsia, gastroesophagal reflux disease, and irritable bowel syndrome; and immunological disorders and inflammation such as atherosclerosis, tendomyopathies and fibromyalgia. In a particular embodiment the disease is cognitive dysfunction associated with schizophrenia also known as cognitive impairment associated with schizophrenia.
[0028] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, can be characterized by X-ray powder diffraction. See the drawing. The peaks were measured using a powder diffractometer equipped with a copper X-ray source, primary beam monochromator, and position sensitive detector. The incident beam was collimated using a 1° divergence slit. The Cu KV source was operated at 45 kV and 40 mA. X-ray powder diffraction data were collected from 3 degrees to 45 degrees in a step width of 0.02 degrees and a time per step of 10 seconds. The diffractometer was well calibrated with a silicon standard. A typical precision of the 2-theta values is in the range of about ±0.2 degrees 2-theta. Thus an X-ray diffraction peak that appears at 8.13 degrees 2-theta can appear between 7.93 and 8.33 degrees 2-theta on typical X-ray diffractometers under standard conditions.
[0029] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, was found to have the following peaks, among others, rounded to 2 significant figures: 8.13, 17.01, 17.49, 18.39, and 20.91 degrees 2-theta, each ±0.2 degrees 2-theta. Form G of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide may be characterized by X-ray diffraction peaks at 8.13 and 18.39 degrees 2-theta, each ±0.2 degrees 2-theta. Thus, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be characterized by peaks at 8.13, 17.01, and 18.39 degrees 2-theta, each ±0.2 degrees 2-theta; by peaks at 8.13, 17.49, and 18.39 degrees 2-theta, each ±0.2 degrees 2-theta; and by peaks at 8.13, 18.39, and 20.91 degrees 2-theta, each ±0.2 degrees 2-theta.
[0030] In addition, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be characterized by peaks at 8.13, 17.01, 17.49, and 18.39 degrees 2-theta, each ±0.2 degrees 2-theta; by peaks at 8.13, 17.01, 18.39, and 20.91 degrees 2-theta, each ±0.2 degrees 2-theta; and by peaks at 8.13, 17.49, 18.39, and 20.91 degrees 2-theta, each ±0.2 degrees 2-theta. 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may also be characterized by peaks at 8.13, 17.01, 17.49, 18.39, and 20.91 degrees 2-theta, each ±0.2 degrees 2-theta.
[0031] It is recognized that the relative intensity of X-ray diffraction peaks can be dependent on preferred orientation and other factors. Although the position of the peak along the 2-theta axis does not change with preferred orientation, the intensity of the peak may change. See, for example, the drawing. Therefore, a sample of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may require processing to mitigate such factors, such as grinding the sample in an agate mortar and pestle or other measures.
[0032] Form G of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide may also be characterized by differential scanning calorimetry. A thermogram of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, provides a single endothermic event at about 214.5° C., which is consistent with a melt. Thermal gravimetric analysis of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, showed no weight loss prior to the melt.
[0033] The present invention also provides a process for making 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, comprising crystallizing 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide.
[0034] The crystallization of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is generally carried out in a solvent or combination of solvents. Suitable solvents may include DMSO, NMP, C 2-4 alkylnitrile, C 3-7 alkylacetate, C 1 -6 alcohol, C 2-8 ether, C 3-7 alkanone, C 6-9 aromatic hydrocarbons, and C 3-5 N, N-dimethylcarboxamide. The crystallization of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is beneficially carried out using an anti-solvent.
[0035] Thus, the selected solvent may contain anti-solvents, that is, a solvent or solvents in which the compound is less soluble than in the selected solvent. Generally, an anti-solvent should be miscible in the selected solvent(s). For example, water may be an anti-solvent for DMSO, NMP, and C 1-6 alcohol; C 2-8 ether, in particular MTBE, may be an anti-solvent for C 2-4 alkylnitrile, C 3-7 alkylacetate, C 1 -6 alcohol, C 2-8 ether, such as THF or 2-MeTHF, C 3-7 alkanone, and C 6-9 aromatic hydrocarbons; and n-heptane may be an anti-solvent for C 3-7 alkylacetate, C 1-6 alcohol, C 2-8 ether, and C 3-7 alkanone.
[0036] Specific solvent/anti-solvent combinations may include the following: MeOH/water, IPA/water, DMSO/water, NMP/water, MeOH/MTBE, EtOH/MTBE, IPA/MTBE, n-BuOH/MTBE, MeCN/MTBE, THF/MTBE, 2-MeTHF/MTBE, MeOAc/MTBE, EtOAc/MTBE, IPAc/MTBE, acetone/MTBE, MEK/MTBE, MIBK/MTBE, DMSO/MTBE, DMF/MTBE, NMP/MTBE, MeOH/n-heptane, EtOH/n-heptane, IPA/n-heptane, n-BuOH/n-heptane, MeCN/n-heptane, THF/n-heptane, 2-MeTHF/n-heptane, MeOAc/n-heptane, EtOAc/n-heptane, IPAc/n-heptane, acetone/n-heptane, MEK/n-heptane, MIBK/n-heptane, DMSO/n-heptane, DMF/n-heptane, and NMP/n-heptane.
[0037] For example, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is crystallized from a solvent. The temperature can range from about 30° C. to up to the reflux temperature of the selected solvent and is usually less than 115° C. The solvent should be one in which 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is somewhat soluble. The volume of solvent is not critical but is typically minimized as a matter of convenience. An anti-solvent may be added to the heated solvent or as the mixture cools. Where the crystallization involves complete dissolution, the rate of cooling is not critical; however, slow cooling is preferred (e.g., cooling at a rate of about 20° C./hour to ambient temperature and then allowed to equilibrate at ambient temperature for about 16 hours). Slurry processing may be used. Optionally, the crystallization may be seeded with 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. According to the present process 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be prepared in substantially pure form.
[0038] In order that the invention may be more fully understood the foregoing processes are exemplified below. These examples are illustrative and are not intended to limit the scope of the invention in any way.
Example 1: 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide
[0039] 1-(1-Methyl-1H-pyrazol-4-yl)-1H-indole-3-carboxylic acid (128.7 g, 0.53 mol) and anhydrous THF (645 mL) was heated to about 43° C. Oxalyl chloride (137.7 g, 92 mL, 1.08 mol) was added dropwise between 40 and 50° C. Gas evolution ceased in approximately 30 minutes. The resulting suspension was stirred for 2 hours at 50° C., allowed to cool to room temperature, and then stirred overnight. The suspension was diluted with heptane (1.5 L), stirred for 10 minutes, and allowed to settle. The supernatant was removed. The addition of heptane (1.5 L), followed by stirring, settling, and decanting was repeated two more times.
[0040] The resulting suspension was diluted with anhydrous THF (645 mL) and the ratio between THF and heptane was determined by NMR to be 3:2. The reaction mixture was cooled to 5° C. and to the mixture was added DIPEA base (138 g, 1.07 mol) at such a rate that the temperature did not exceed 20° C. Next (1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-amine (101.4 g, 0.63 mol) in 500 mL of anhydrous THF was added. The reaction mixture was warmed to ambient temperature and stirred at 20 to 23° C. overnight to give a suspension.
[0041] The suspension was filtered and the cake was dissolved in 1N HCl (2.6 L). The aqueous layer was washed with EtOAc (3×2.6 L). The aqueous layer was cooled to 5° C. and was basified to pH 12 with aqueous potassium hydroxide (230 g) solution in water (500 mL). The mixture was stirred at 5 to 10° C. overnight to give a solid. The product was filtered, washed with water (2×1.2 L), followed by MTBE (2×1.2 L), and then dried to give 128 g (64%) of the (crude) title compound.
Example 2: 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide
[0042] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (17 g, 44.8 mmol) in EtOAc (500 mL) and 250 mL of HCl/EtOAc (4M) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was then concentrated to dryness to give 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7s)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, bis-hydrogen chloride salt (18 g, 39.8 mmol, 89% yield).
[0043] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7s)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, bis-hydrogen chloride salt was combined with DMSO (80 mL) and the mixture was heated in oil bath to 50° C. until a homogeneous solution was formed. An aqueous sodium hydroxide solution (4M, 9.28 mL, 37.1 mmol) was added via addition funnel over 3 minutes. After stirring for 5 minutes, water (80 mL) was added slowly via addition funnel over 10 minutes at 50° C. After the water addition was completed the internal temp was kept at 51° C. The reaction was stirred at 50° C. for 1 hour and then cooled to room temperature over 3 hour period to give a solid. The solid was collected by filtration, washed with water (24 mL), air dried for 1 hour, followed by vacuum oven drying at 50° C. overnight to give a hydrate of the title compound.
Example 3: 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0044] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7s)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (300 mg, 0.791 mmol) was combined with DMSO (2.1 mL) and was heated on reaction block to 80° C. with stirring. Water (3.90 mL) was added slowly via syringe in 3 portions over 15 minutes. The reaction was stirred at 80° C. for 30 minutes before slowly cooled to room temperature over 4 hours and stirred overnight at room temperature to give a solid. The solid was collected by filtration, washed with water (3×2 mL), air dried for 1 hour, followed by high vacuum drying at room temperature for 4 hours to give the title compound.
Example 4: 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0045] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (25.9 mg) and DMSO (0.4 mL) were combined and heated to 70° C. Water (0.6 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 5 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0046] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (25.9 mg) and DMSO (0.4 mL) were combined and heated to 70° C. Water (0.6 mL) was added and the mixture was cooled to ambient temperature at a rate of 20° C. per hour and allowed to equilibrate with stirring at ambient temperature over 16 hours. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 6 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0047] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (31.0 mg) and MeOH (1.0 mL) were combined and heated to 60° C. MTBE (2.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 7 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0048] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (29.8 mg) and MeCN (1.0 mL) were combined and heated to 70° C. MTBE (2.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 8 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0049] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (30.6 mg) and THF (0.5 mL) were combined and heated to 70° C. MTBE (1.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 9 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0050] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (27.5 mg) and toluene (2.0 mL) were combined and heated to 70° C. MTBE (4.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 10 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0051] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (26.5 mg) and acetone (0.5 mL) were combined and heated to 60° C. MTBE (1.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 11 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0052] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (29.3 mg) and EtOH (0.5 mL) were combined and heated to 70° C. MTBE (1.0 mL) was added and the mixture was cooled to ambient temperature at a rate of 20° C. per hour and allowed to equilibrate with stirring at ambient temperature over 16 hours. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 12 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0053] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (27.8 mg) and IPA (0.5 mL) were combined and heated to 70° C. MTBE (1.0 mL) was added and the mixture was cooled to ambient temperature at a rate of 20° C. per hour and allowed to equilibrate with stirring at ambient temperature over 16 hours. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 13 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0054] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (31.4 mg) and acetone (0.5 mL) were combined and heated to 50° C. Heptane (1.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 14 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0055] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (34.5 mg) and EtOH (1.0 mL) were combined and heated to 70° C. Heptane (2.0 mL) was added and the mixture was cooled to ambient temperature at a rate of 20° C. per hour and allowed to equilibrate with stirring at ambient temperature over 16 hours. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 15 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0056] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (58.3 mg) and IPA (1.0 mL) were combined and heated to 70° C. MTBE (2.0 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 16 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0057] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (61.5 mg) and acetone (1.0 mL) were combined and heated to 60° C. MTBE (1.5 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 17 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0058] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (27.4 mg) and IPA (1.0 mL) were combined and heated to 70° C. Water (1.5 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 18 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0059] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (24.3 mg) and NMP (1.0 mL) were combined and heated to 70° C. Water (0.6 mL) was added and the mixture was stored at 4° C. overnight. The solids were collected by centrifugation, dried in vacuo at ambient temperature to give the title compound.
Example 19 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G
[0060] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide (126 g) was dissolved in a mixture of denatured ethanol, containing 5% methanol and 5% isopropanol (1070 mL), and DMSO (1070 mL) at 70° C. and stirred for 1 hour. The resulting solution was filtered through a paper filter, reheated to 70° C., and then cooled to 50° C. over 30 minutes. Seeds of Form G (1.3 g) were added. The temperature was raised to 70° C., and then cooled to 50° C. over 30 minutes. Seeds of Form G (1.3 g) were again added and the resulting suspension was cooled to 40° C. over 30 minutes and kept at this temperature with stirring for 5 hours. The resulting suspension was then cooled to 5° C. over 1 hour and was stirred at this temperature for 6 hours. The resulting solid was collected by filtration, washed with ethanol (2×250 mL), and dried under vacuum over 3 days at 40° C. to give the title compound.
[0061] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is a 5-HT3 inhibitor. Receptors of 5-HT3 are known to be expressed in the central nervous system in regions involving vomiting reflex, processing of pain, cognition and anxiety control and play a role in the pathogenesis of diseases such as emesis, migraine, drug addiction, and neurodegenerative and psychiatric disorders such as anxiety and depression (see Hewlett et al., 2003 J. Clin. Psychiatry 64, 1025-1030; Kelley et al., 2003a, Eur J. Pharmacol., 461, 19-25; Haus et al., 2000 Scand J Rheumatol Suppl 113, 55-58; and Faris et al., 2006 J affect Disorder 92, 79-90), eating disorders (Hammer et al., 1990 Am J Physiol 259, R627-R636, and Jiang & Gietzen 1994 Pharmacol Biochem Behav 47, 59-63), schizophrenia (see Hermann et al. 1996 Biochem Biophys Res Commun 225, 957-960; Sirota et al., 2000 Am J Psychiatry 157, 287-289; Adler et al., 2005 Am J Psychiatry 162, 386-388; Koike et al., Levkovitz et al, 2005 Schizophr Res 76, 67-72), cognitive dysfunction associated with schizophrenia (see Zhang et al., 2006 Schizophr Res 88, 102-110; Akhondzadeh et al., 2009 Schizophr Res 107, 206-212), cognitive dysfunction associated with Parkinson's disease, Huntington's Chorea, presenile dementias and Alzheimer's disease (see Costall and Naylor 2004 CNS Neurol Disord 3, 27-37) substance abuse and addiction (see Johnson et al., 2002 Psycho-pharmacology (Berl) 160, 408-413; Johnson, 2004 CNS Drugs 18, 1105-1118; Dawes et al., 2005 Addict Behav 30, 1630-1637, Johnson 2006 Drug Alcohol Depend 84, 256-263), and pain (see Kayser et al, 2007 Pain 130, 235; Glaum et al., 1998 Neurosci Lett 95, 313-317; Schworer & Ramadori 1993 Clin Investig 71, 659; Thompson and Lummis 2007 Exp Opin Ther Targets, 11, 527-540). In addition, 5-HT3 receptors are expressed in the GI tract and hence may play a role in GI disorders such as dyspepsia, gastroesophagal reflux disease and irritable bowel syndrome (see Graeff 1997 Psychiatr Clin North Am 20, 723; Thompson and Lummis 2007 Exp Opin Ther Targets, 11, 527-540; Barnes et al. 2009 Neuropharmacology 56, 273). Expression of the 5-HT3A subunit has also been discovered extraneuronally in immune cells such as monocytes, chondrocytes, T-cells, synovial tissue and platelets (Fiebich et al., 2004 Scan J Rheumatol Suppl, 9-11, Stratz et al., 2008 Thromb Haemost 99, 784) and of 5-HT3A, C-E within the lamina propia in the epithelium of the gut mucose (Kapeller et al., J Comp Neuro, 2008; 509: 356-371) thus suggesting they may be involved in immunological and inflammatory diseases like atherosclerosis, tendomyopathies and fibromyalgia.
[0062] The 5-HT3 inhibitory activity of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be tested using the in vitro assay and in vivo assay described in PCT Publication No. WO 2014/014951, published Jan. 23, 2014.
[0063] In general, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, will be administered in a therapeutically effective amount by any of the accepted modes of administration for agents that serve similar utilities. Therapeutically effective amounts of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may range from about 0.01 to about 75 mg per kg patient body weight per day, which can be administered in single or multiple doses. Preferably, the dosage level will be about 0.01 to about 10 mg/kg per day; more preferably about 0.5 to about 5 mg/kg per day or 0.1-2 mg/kg/day. For oral administration, the compositions are preferably provided in the form of tablets containing about 0.5 to about 200 milligrams of the active ingredient, from about 0.5, 1.0, 5.0, 10, 15, 20, 25, 50, 75, 100, 150, or 200 milligrams of the active ingredient. The actual amount of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, i.e., the active ingredient, will depend upon numerous factors such as the severity of the disease to be treated, the age and relative health of the subject, the route and form of administration, and other factors. Although these dosages are based on an average human subject having a mass of about 60 kg to about 70 kg, the physician will be able to determine the appropriate dose for a patient (e.g., an infant) whose mass falls outside of this weight range.
[0064] In general, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, will be administered as pharmaceutical compositions by any one of the following routes: oral, systemic (e.g., transdermal, intranasal or by suppository), or parenteral (e.g., intramuscular, intravenous or subcutaneous) administration. The preferred manner of administration is oral dosing using a convenient daily dosage regimen, which can be adjusted according to the degree of affliction. Compositions can take the form of tablets, pills, capsules, semisolids, powders, sustained release formulations, solutions, suspensions, elixirs, aerosols, or any other appropriate compositions.
[0065] The choice of formulation depends on various factors such as the mode of drug administration (e.g., for oral administration, formulations in the form of tablets, pills or capsules are preferred) and the bioavailability of the drug substance. Recently, pharmaceutical formulations have been developed especially for drugs that show poor bioavailability based upon the principle that bioavailability can be increased by increasing the surface area i.e., decreasing particle size. For example, U.S. Pat. No. 4,107,288 describes a pharmaceutical formulation having particles in the size range from 10 to 1,000 nm in which the active material is supported on a crosslinked matrix of macromolecules. U.S. Pat. No. 5,145,684 describes the production of a pharmaceutical formulation in which the drug substance is pulverized to nanoparticles (average particle size of 400 nm) in the presence of a surface modifier and then dispersed in a liquid medium to give a pharmaceutical formulation that exhibits remarkably high bioavailability.
[0066] The compositions are comprised of in general, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, in combination with at least one pharmaceutically acceptable excipient. Acceptable excipients are non-toxic, aid administration, and do not adversely affect the therapeutic benefit of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. Such excipient may be any solid, liquid, semi-solid or, in the case of an aerosol composition, gaseous excipient that is generally available to one of skill in the art.
[0067] Solid pharmaceutical excipients include starch, cellulose, talc, glucose, lactose, sucrose, gelatin, malt, rice, flour, chalk, silica gel, magnesium stearate, sodium stearate, glycerol monostearate, sodium chloride, dried skim milk and the like. Liquid and semisolid excipients may be selected from glycerol, propylene glycol, water, ethanol and various oils, including those of petroleum, animal, vegetable or synthetic origin, e.g., peanut oil, soybean oil, mineral oil, sesame oil, etc. Preferred liquid carriers, particularly for injectable solutions, include water, saline, aqueous dextrose, and glycols.
[0068] Compressed gases may be used to disperse 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, in aerosol form. Inert gases suitable for this purpose are nitrogen, carbon dioxide, etc.
[0069] Other suitable pharmaceutical excipients and their formulations are described in Remington's Pharmaceutical Sciences, edited by E. W. Martin (Mack Publishing Company, 18th ed., 1990).
[0070] The level of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, in a formulation can vary within the full range employed by those skilled in the art. Typically, the formulation will contain, on a weight percent (wt %) basis, from about 0.01-99.99 wt % of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, based on the total formulation, with the balance being one or more suitable pharmaceutical excipients. Preferably, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is present at a level of about 1-80 wt %.
[0071] 1-(1-Methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be used in combination with one or more other drugs in the treatment of diseases or conditions for which 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, or the other drugs may have utility, where the combination of the drugs together are safer or more effective than either drug alone. Such other drug(s) may be administered, by a route and in an amount commonly used therefore, contemporaneously or sequentially with 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. When 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, is used contemporaneously with one or more other drugs, a pharmaceutical composition in unit dosage form containing such other drugs and 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be used. However, the combination therapy may also include therapies in which 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, and one or more other drugs are administered on different overlapping schedules. It is also contemplated that when used in combination with one or more other active ingredients, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, and the other active ingredients may be used in lower doses than when each is used singly.
[0072] Accordingly, the pharmaceutical compositions of the present invention also include those that contain one or more other active ingredients, in addition to 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G.
[0073] The above combinations include combinations of 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, not only with one other active compound, but also with two or more other active compounds. Likewise, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be used in combination with other drugs that are used in the prevention, treatment, control, amelioration, or reduction of risk of the diseases or conditions for which 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, are useful. Such other drugs may be administered, by a route and in an amount commonly used therefore, contemporaneously or sequentially with 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. Accordingly, the pharmaceutical compositions of the present invention also include those that also contain one or more other active ingredients, in addition to 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G. The weight ratio of the 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, to the second active ingredient may be varied and will depend upon the effective dose of each ingredient. Generally, an effective dose of each will be used.
[0074] In one embodiment, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with anti-Alzheimer's agents, beta-secretase inhibitors, gamma-secretase inhibitors, HMG-CoA reductase inhibitors, NSAID's including ibuprofen, vitamin E, and anti-amyloid antibodies. In another embodiment, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with sedatives, hypnotics, anxiolytics, antipsychotics, antianxiety agents, cyclopyrrolones, imidazopyridines, pyrazolopyrimidines, minor tranquilizers, melatonin agonists and antagonists, melatonergic agents, benzodiazepines, barbiturates, mGlu2/3 agonists, 5HT-2 antagonists, PDE10 antagonists, GlyT1 inhibitors, and the like, such as: adinazolam, allobarbital, alonimid, alprazolam, amisulpride, amitriptyline, amobarbital, amoxapine, aripiprazole, bentazepam, benzoctamine, brotizolam, bupropion, busprione, butabarbital, butalbital, capuride, carbocloral, chloral betaine, chloral hydrate, clomipramine, clonazepam, cloperidone, clorazepate, chlordiazepoxide, clorethate, chlorpromazine, clozapine, cyprazepam, desipramine, dexclamol, diazepam, dichloralphenazone, divalproex, diphenhydramine, doxepin, estazolam, ethchlorvynol, etomidate, fenobam, flunitrazepam, flupentixol, fluphenazine, flurazepam, fluvoxamine, fluoxetine, fosazepam, glutethimide, halazepam, haloperidol, hydroxyzine, imipramine, lithium, lorazopam, lormetazepam, maprotiline, mecloqualone, melatonin, mephobarbital, meprobamate, methaqualone, midaflur, midazolam, nefazodone, nisobamate, nitrazopam, nortriptyline, olanzapine, oxazepam, paraldehyde, paroxetine, pentobarbital, perlapine, perphenazine, phenelzine, phenobarbital, prazepam, promethazine, propofol, protriptyline, quazepam, quetiapine, reclazepam, risperidone, roletamide, secobarbital, sertraline, suproclone, temazopam, thioridazine, thiothixene, tracazolate, kanylcypromaine, trazodone, triazolam, trepipam, tricetamide, triclofos, trifluoperazine, trimetozine, trimipramine, uldazepam, venlafaxine, zaleplon, ziprasidone, zolazepam, zolpidem, [4-(3-fluoro-5-trifluoromethylpyridin-2-yl)piperazin-1-yl][5-methanesulfonyl-2-((S)-2,2,2-trifluoro-1-methylethoxy)phenyl]methanone (RG1678), glyt1 inhibitors disclosed in U.S. Pat. No. 7,538,114, Table 1 in column 14, and salts thereof, and combinations thereof.
[0075] In another embodiment, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with levodopa (with or without a selective extracerebral decarboxylase inhibitor such as carbidopa or benserazide), anticholinergics such as biperiden (optionally as its hydrochloride or lactate salt) and trihexyphenidyl (benzhexol) hydrochloride, COMT inhibitors such as entacapone, MOA-B inhibitors, antioxidants, A2a adenosine receptor antagonists, cholinergic agonists, NMDA receptor antagonists, serotonin receptor antagonists and dopamine receptor agonists such as alentemol, bromocriptine, fenoldopam, lisuride, naxagolide, pergolide and prarnipexole. It will be appreciated that the dopamine agonist may be in the form of a pharmaceutically acceptable salt, for example, alentemol hydrobromide, bromocriptine mesylate, fenoldopam mesylate, naxagolide hydrochloride and pergolide mesylate. Lisuride and pramipexol are commonly used in a non-salt form.
[0076] In another embodiment, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with a compound from the phenothiazine, thioxanthene, heterocyclic dibenzazepine, butyrophenone, diphenylbutylpiperidine and indolone classes of neuroleptic agent. Suitable examples of phenothiazines include chlorpromazine, mesoridazine, thioridazine, acetophenazine, fluphenazine, perphenazine and trifluoperazine. Suitable examples of thioxanthenes include chlorprothixene and thiothixene. An example of a dibenzazepine is clozapine. An example of a butyrophenone is haloperidol. An example of a diphenylbutylpiperidine is pimozide. An example of an indolone is molindolone. Other neuroleptic agents include loxapine, sulpiride and risperidone. It will be appreciated that the neuroleptic agents when used in combination with 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be in the form of a pharmaceutically acceptable salt, for example, chlorpromazine hydrochloride, mesoridazine besylate, thioridazine hydrochloride, acetophenazine maleate, fluphenazine hydrochloride, flurphenazine enathate, fluphenazine decanoate, trifluoperazine hydrochloride, thiothixene hydrochloride, haloperidol decanoate, loxapine succinate and molindone hydrochloride. Perphenazine, chlorprothixene, clozapine, haloperidol, pimozide and risperidone are commonly used in a non-salt form. Thus, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with acetophenazine, alentemol, aripiprazole, amisulpride, benzhexol, bromocriptine, biperiden, chlorpromazine, chlorprothixene, clozapine, diazepam, fenoldopam, fluphenazine, haloperidol, levodopa, levodopa with benserazide, levodopa with carbidopa, lisuride, loxapine, mesoridazine, molindolone, naxagolide, olanzapine, pergolide, perphenazine, pimozide, pramipexole, quetiapine, risperidone, sulpiride, tetrabenazine, trihexyphenidyl, thioridazine, thiothixene, trifluoperazine or ziprasidone.
[0077] In another embodiment, 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, may be administered in combination with an anti-depressant or anti-anxiety agent, including norepinephrine reuptake inhibitors (including tertiary amine tricyclics and secondary amine tricyclics), selective serotonin reuptake inhibitors (SSRIs), monoamine oxidase inhibitors (MAOIs), reversible inhibitors of monoamine oxidase (RIMAs), serotonin and noradrenaline reuptake inhibitors (SNRls), corticotropin releasing factor (CRF) antagonists, adrenoreceptor antagonists, neurokinin-1 receptor antagonists, atypical anti-depressants, benzodiazopines, 5-HTA agonists or antagonists, especially 5-HTA partial agonists, and corticotropin releasing factor (CRF) antagonists. Specific agents include: amitriptyline, clomipramine, doxepin, imipramine and trimipramine; amoxapine, desipramine, maprotiline, nortriptyline and protriptyline; fluoxetine, fluvoxamine, paroxetine and sertraline; isocarboxazid, phenelzine, tranylcypromine and selegiline; moclobemide, venlafaxine; duloxetine; aprepitant; bupropion, lithium, nefazodone, trazodone and viloxazine; alprazolam, chlordiazepoxide, clonazopam, chlorazepate, diazopam, halazepam, lorazepam, oxazopam and prazepam; buspirone, flesinoxan, gepirone and ipsapirone, and pharmaceutically acceptable salts thereof.
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Disclosed is a crystalline polymorph 1-(1-methyl-1H-pyrazol-4-yl)-N-((1R,5S,7S)-9-methyl-3-oxa-9-azabicyclo[3.3.1]nonan-7-yl)-1H-indole-3-carboxamide, Form G, and processes for making the same
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FIELD OF THE INVENTION
The present invention relates to a variable displacement swash plate type compressor adapted for use in an air conditioning system for a vehicle, and more particularly to a compressor conduit means for pressurizing a crankcase to control the displacement of the swash plate of the compressor, and for facilitating lubrication of compressor components.
BACKGROUND OF THE INVENTION
Variable displacement swash plate type compressors typically include a cylinder block provided with a number of cylinders, a piston disposed in each of the cylinders of the cylinder block, a crankcase sealingly disposed on one end of the cylinder block, a rotatably supported drive shaft, and a swash plate. The swash plate is adapted to be rotated by the drive shaft. Rotation of the swash plate is effective to reciprocatively drive the pistons. The length of the stroke of the pistons is varied by the inclination of the swash plate. Inclination of the swash plate is varied by controlling the pressure differential between a suction chamber and a crank chamber. The pressure differential is typically controlled using a control valve and an orifice tube which facilitates fluid communication between a discharge chamber and the crank chamber to convey compressed gases from the discharge chamber to the crank chamber based on pressure in a suction chamber.
The compressor arrangement in the prior art described above has several disadvantages. First, due to the introduction of refrigerant gas through the orifice tube into the crank chamber, the pressure within the crank chamber cannot be accurately controlled. Second, when the compressor is operating at maximum capacity, the control valve closes, thereby eliminating flow through the orifice tube. Therefore, ineffective lubrication of the close tolerance moving parts within the crank chamber occurs due to the lack of consistent flow of refrigerant gas from the discharge chamber to the crank chamber. Finally, the tight tolerances required in the orifice tube are difficult to achieve in manufacturing due to the small diameter of the orifice tube.
An object of the present invention is to produce a swash plate type compressor wherein the pressure within the crankcase is increased and efficiently controlled.
Another object of the present invention is to produce a swash plate type compressor wherein oil flow to the crankcase during both minimum and maximum operating conditions is facilitated to result in improved lubrication of the compressor components.
SUMMARY OF THE INVENTION
The above, as well as other objects of the invention, may be readily achieved by a variable displacement swash plate type compressor comprising: a cylinder block having a plurality of cylinders arranged radially therein; a piston reciprocatively disposed in each of the cylinders of the cylinder block; a cylinder head attached to the cylinder block; a crankcase cooperating with the cylinder block to define a crank chamber; a drive shaft rotatably supported by the crankcase and the cylinder block; a swash plate adapted to be driven by the drive shaft, the swash plate having a central aperture for receiving the drive shaft, radially outwardly extending side walls, and a peripheral edge; and conduit means providing fluid communication between the crank chamber and at least one of the cylinders of the cylinder block.
BRIEF DESCRIPTION OF THE DRAWINGS
The above, as well as other objects, features, and advantages of the present invention will be understood from the detailed description of the preferred embodiment of the present invention with reference to the accompanying drawings, in which:
FIG. 1 is a cross sectional elevational view of a variable displacement swash plate type compressor incorporating the features of the invention, showing a conduit in fluid communication with the crank chamber and one cylinder;
FIG. 2 is a perspective view of the cylinder block of the compressor illustrated in FIG. 1 showing the features of the invention, the bore portion of the conduit is illustrated by a phantom line;
FIG. 3 is a graph illustrating the relationship between the pressure in the crank chamber, discharge chamber, suction chamber, and cylinder during one revolution of the compressor;
FIG. 4 is a graph illustrating the relationship between the net flow of refrigerant gas from a cylinder into the crank chamber for a prior art compressor having an orifice tube, and the net flow of refrigerant gas from a cylinder into the crank chamber for a compressor incorporating the conduit of the present invention;
FIG. 5 is a graph illustrating the relationship between flow rate of refrigerant gas for a prior art compressor having an orifice tube, and the flow rate of refrigerant gas for a compressor incorporating the conduit of the present invention;
FIG. 6 is a perspective view of an alternate embodiment of the invention of FIG. 1 schematically showing a ball type valve in the conduit of the cylinder block; and
FIG. 7 is a partial cross sectional elevational view of the embodiment illustrated in FIG. 6 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, and particularly FIG. 1, there is shown generally at 10 a variable displacement swash plate type compressor incorporating the features of the invention. The compressor 10 includes a cylinder block 12 having a plurality of cylinders 14 . A cylinder head 16 is disposed adjacent one end of the cylinder block 12 and sealingly closes the end of the cylinder block 12 . A valve plate 18 is disposed between the cylinder block 12 and the cylinder head 16 . A crankcase 20 is sealingly disposed at the other end of the cylinder block 12 . The crankcase 20 and cylinder block 12 cooperate to form an airtight crank chamber 22 .
The cylinder head 16 includes a suction chamber 24 and a discharge chamber 26 . An inlet port 28 and associated inlet conduit 30 provide fluid communication between the evaporator (not shown) of the cooling portion of the air conditioning system for a vehicle and the suction chamber 24 . An outlet port 32 and associated outlet conduit 34 provide fluid communication between the discharge chamber 26 and the cooling portion of the air conditioning system for a vehicle. Suction ports 36 provide fluid communication between the suction chamber 24 and each cylinder 14 . Each suction port 36 is opened and closed by a suction valve 37 . Discharge ports 38 provide fluid communication between each cylinder 14 and the discharge chamber 26 . Each discharge port 38 is opened and closed by a discharge valve 39 . A retainer 40 restricts the opening of the discharge valve 39 .
A drive shaft 41 is centrally disposed in and arranged to extend through the crankcase 20 to the cylinder block 12 . The drive shaft 41 is rotatably supported in the crankcase 20 .
A rotor 42 is fixedly mounted on an outer surface of the drive shaft 41 adjacent one end of the crankcase 20 within the crank chamber 22 . An arm 44 extends outwardly from a surface of the rotor 42 opposite the surface of the rotor 42 that is adjacent the end of the crankcase 20 . A slot 46 is formed in the distal end of the arm 44 . A pin 48 has one end slidingly disposed in the slot 46 of the arm 44 of the rotor 42 .
A swash plate 50 is formed to include a hub 52 and an annular plate 54 with a peripheral marginal edge 56 . The hub 52 includes an annular main body 58 with a centrally disposed aperture 60 formed therein and an arm 62 that extends outwardly and perpendicularly from the surface of the hub 52 . An aperture 64 is formed in the distal end of the arm 62 of the hub 52 . One end of the pin 48 is slidingly disposed in the slot 46 of the arm 44 of the rotor 42 , while the other end is fixedly disposed in the aperture 64 of the arm 62 .
A hollow annular extension 66 extends from the opposite surface of the hub 52 as the arm 62 . Two holes 68 , 70 are formed in the annular extension 66 of the hub 52 . Two pins 72 , 74 are disposed in the holes 68 , 70 , respectively. A portion of the outer surface of the pins 72 , 74 extend inwardly within the hollow annular extension 66 of the hub 52 .
The annular plate 54 has a centrally disposed aperture 76 formed therein to receive the annular extension 66 of the hub 52 . The annular extension 66 is press fit in the aperture 76 of the annular plate 54 . The drive shaft 41 is adapted to extend through the hollow annular extension 66 .
A helical spring 78 is disposed to extend around the outer surface of the drive shaft 41 . One end of the spring 78 abuts the rotor 42 , while the opposite end abuts the hub 52 of the swash plate 50 .
A piston 80 is slidably disposed in each of the cylinders 14 in the cylinder block 12 . Each piston 80 includes a head 82 , a middle portion 84 , and a bridge portion 86 . A compression chamber 87 is formed between the head 82 of piston 80 and the valve plate 18 . A circumferential groove 88 is formed in an outer cylindrical wall of the head 82 to receive piston rings (not shown). The middle portion 84 terminates in the bridge portion 86 defining an interior space 90 for receiving the peripheral marginal edge 56 of the annular plate 54 . Spaced apart concave pockets 92 are formed in the interior space 90 of the bridge portion 86 for rotatably containing a pair of semi-spherical shoes 94 . The spherical surfaces of the shoes 94 are disposed in the shoe pockets 92 with a flat bearing surface disposed opposite the spherical surface for slidable engagement with the opposing sides of the annular plate 54 .
A channel or conduit 96 , illustrated in FIGS. 1 and 2, is disposed between the crank chamber 22 and one of the cylinders 14 . The conduit 96 is formed by a bore portion 98 and a slot portion 100 . The bore portion 98 extends longitudinally through the cylinder block 12 adjacent and substantially parallel to one of the cylinders 14 . The slot portion 100 is formed in the surface of the cylinder block 12 adjacent to the valve plate 18 , and extends laterally from one of the cylinders 14 to the bore portion 98 . The conduit 96 provides direct fluid communication between the crank chamber 22 and the compression chamber 87 of one of the cylinders 14 . In FIG. 2, only one cylinder is illustrated by a phantom line, however it is understood that the embodiment cylinder block illustrated includes six cylinders.
In an alternate embodiment, a control valve 102 ′ may be disposed in the conduit 96 ′ for controlling the flow of refrigerant gas from the cylinder 14 ′ to the crank chamber 22 , as illustrated in FIGS. 6 and 7. It should be noted that the conduit 96 ′ is rotated from the location of FIG. 2 in order to accommodate the control valve 102 ′. The control valve 102 ′ may be of any conventional type such as, for example, a ball type valve. The control valve 102 ′ may be adapted to receive a signal from a remote source to vary the flow of the refrigerant gas therethrough. Either a mechanical or electronic type control valve may be used. The mechanical type control valve can be arranged to receive either a temperature or pressure control signal from an evaporator in the air conditioning system of a vehicle. Alternatively, the electronic type control valve is arranged to receive an electrical signal from a microprocessor. The microprocessor for the electronic type control valve monitors the discharge pressure of the compressor, the RPM of the vehicle engine, and the like, to control the flow of refrigerant gas from the one of the cylinders 14 ′, through the conduit 96 ′, and to the crank chamber 22 .
The operation of the compressor 10 is accomplished by rotation of the drive shaft 41 by an auxiliary drive means (not shown), which may typically be the internal combustion engine of a vehicle. Rotation of the drive shaft 41 causes the rotor 42 to correspondingly rotate with the drive shaft 41 . The swash plate 50 is connected to the rotor 42 by a hinge mechanism formed by the pin 48 slidingly disposed in the slot 46 of the arm 44 of the rotor 42 and fixedly disposed in the aperture 64 of the arm 62 of the hub 52 . As the rotor 42 rotates, the connection made by the pin 48 between the swash plate 50 and the rotor 42 causes the swash plate 50 to rotate. During rotation, the swash plate 50 is disposed at an inclination. The rotation of the swash plate 50 is effective to reciprocatively drive the pistons 80 . The rotation of the swash plate 50 further causes a sliding engagement between the opposing sides of the annular plate 54 and the cooperating spaced apart shoes 94 . The reciprocation of the pistons 80 causes refrigerant gas to be introduced from the suction chamber 22 into the respective cylinders 14 of the cylinder head 16 . The reciprocating motion of the pistons 80 then compresses the refrigerant gas within each cylinder 14 . When the pressure within each cylinder 14 exceeds the pressure within the discharge chamber 26 , the compressed refrigerant gas is discharged into the discharge chamber 26 .
The capacity of the compressor 10 can be changed by changing the inclination of the swash plate 50 and thereby changing the length of the stroke for the pistons 80 . The inclination of the swash plate 50 is changed by controlling the pressure differential between the crank chamber 22 and the suction chamber 24 . The pressure differential is controlled by controlling the net flow of refrigerant gas from the at least one cylinder 14 to the crank chamber 22 through the conduit 96 .
Specifically, as the piston 80 is caused to move toward a bottom dead center position, the pressure within the cylinder 14 is less than the pressure within the suction chamber 24 . The suction valve 37 is caused to open causing refrigerant gas to flow into the cylinder 14 through the suction port 36 . As illustrated in FIG. 3, the pressure within the crank chamber 22 remains at a level between the pressure within the suction chamber 24 and the pressure within the discharge chamber 26 during rotation of the drive shaft 41 .
Conversely, as the piston 80 is caused to move toward a top dead center position, the refrigerant gas within the cylinder 14 is compressed until the pressure within the cylinder 14 is caused to exceed the pressure within the discharge chamber 26 . The discharge valve 39 is caused to open and refrigerant gas is caused to flow through the discharge port 38 to the discharge chamber 26 .
Further, as the piston 80 is caused to move toward a bottom dead center position within the at least one cylinder 14 , the pressure within the cylinder 14 is less than the pressure within the crank chamber 22 , causing refrigerant gas to flow through the conduit 96 to the cylinder 14 . As the piston 80 is caused to move toward a top dead center position, the refrigerant gas within the cylinder 14 is compressed causing the pressure within the cylinder 14 to increase and exceed the pressure within the crank chamber 22 . When the pressure within the cylinder 14 exceeds the pressure within the crank chamber 22 , refrigerant gas is caused to flow through the conduit 96 to the crank chamber 22 . Additionally, as the refrigerant gas within the cylinder 14 is compressed, the net flow and the rate of flow of refrigerant gas from the cylinder 14 to the crank chamber 22 are increased and become positive, as illustrated in FIGS. 4 and 5.
By introducing the refrigerant gas from the cylinder 14 into the crank chamber 22 through the conduit 96 , instead of introducing the refrigerant gas from the discharge chamber 26 into the crank chamber 22 through an orifice tube, several benefits are apparent. The capacity and efficiency of the compressor 10 have been maximized. The orifice tube of prior art compressors bypasses compressed refrigerant gas from the discharge chamber 26 to the crank chamber 22 , thereby preventing the compressed gas from being used in the cooling portion of the air conditioning system for a vehicle. By creating a conduit communicating the crank chamber 22 and the one of the cylinders 14 , the flow of refrigerant gas from the cylinder 14 into the crank chamber 22 is efficiently controlled. Rather than bleeding highly pressurized refrigerant gas from the discharge chamber 26 into the crank chamber 22 , the net flow of refrigerant gas is from the one of the cylinders 14 into the crank chamber 22 . Because refrigerant gas flows from the cylinder 14 to the crank chamber 22 before the pressure of the refrigerant gas reaches the higher pressure within the discharge chamber 26 , the net flow of refrigerant gas into the crank chamber 22 occurs at a lower pressure than with a prior art orifice tube.
An additional benefit of the present invention is that oil present in the refrigerant gas provides lubrication to the close tolerance moving components of the compressor 10 . The lubrication maximizes the durability of the compressor 10 .
Finally, by introducing the refrigerant gas to the crank chamber 22 through the conduit 96 , the orifice tube of prior art is eliminated.
Use of the control valve 102 of the alternate embodiment controls the flow of refrigerant gas between the cylinder 14 and the crank chamber 22 . Only unidirectional flow is permitted from the cylinder 14 to the crank chamber 22 .
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A variable displacement swash plate type compressor which incorporates a conduit formed in the cylinder block to provide fluid communication between a crank chamber and one or more cylinders to eliminate the need for an orifice tube in fluid communication between a discharge chamber and the crank chamber and to increase the flow of refrigerant gas and lubricating oil to the crank chamber under all operating conditions and to increase the internal fluid pressure in the crank chamber.
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CROSS REFERENCE TO RELATED APPLICATIONS
Details of the draw bar structure and of the circle mounting bar and circle assembly which are illustrated and described generally in this application are described in detail and claimed in copending U.S. patent applications of Carroll Richard Cole, Ser. No. 661,880, filed Feb. 27, 1976, issued Dec. 27, 1977 as U.S. Pat. No. 4,064,947 and Ser. No. 663,594, filed Mar. 3, 1976 issued Apr. 5, 1977 as U.S. Pat. No. 4,015,669.
BACKGROUND OF THE INVENTION
Motor graders have a longitudinal main frame which has a dirigible wheel assembly at its forward end, an operator's cab at its rearward end portion, and a traction chassis for the motor and power train behind the cab. The motor grader blade is suspended from the main frame by means of a circle draw bar and a circle. The circle draw bar has its front end connected to the front of the main frame by a ball and socket connection, while the rearward portion of the circle draw bar is suspended from the main frame by hydraulic cylinder and piston means which permit the draw bar to swing in a vertical plane about its front end.
The rearward portion of the circle draw bar constitutes a circle carrying structure, and a circle is supported beneath the carrying structure for rotation about a vertical axis. An internal gear, which is preferably a spur gear because of the relative ease of manufacture, is secured to the circle, and the internal gear and circle are driven by a hydraulic motor through a power train which commonly terminates in a pinion of one sort or another engaging the internal gear.
Two types of prior art circle drives which are known to applicant are disclosed in U.S. Pat. Nos. 2,928,381 and 3,911,758.
There are a number of problems with prior art which drives an internal gear of a motor grader circle from a pinion. Perhaps the most serious is that the forces imposed at the tip of an extended motor grader blade are carried back through the internal gear to the pinion and then to the power input for the spur gear. With a typical motor grader having a maximum extended blade reach of 10 1/2 feet and a circle of 30 inch radius can produce a contact stress in excess of 700,000 psi on the circle drive pinion. This is sufficient to cause metal to extrude away from the contact area and permanently deform the tooth surfaces. Since the only ultimate braking effort is provided by the input worm drive, substantial damage may be sustained by those components.
Another problem in conventional pinion drives for motor grader circles involves the inherent variations in backlash of the pinion to circle mesh. Where the pinion tooth is nearly at the bottom of the tooth's base, there is almost no backlash, while with the pinion rotated approximately half way from the internal gear tooth dedendum to the internal gear tooth addendum the backlash may be about 0.22 inch even before there has been any tooth wear. This permits the induced blade forces to set up vibrations in the circle and the blade mechanism, as well as in the related structure, which substantially reduces the fatigue life of components. The backlash also causes impact loading on the circle drive mesh which further increases the contact stress and produces further damaging forces in the entire circle drive mechanism. Excessive backlash also causes poor surface finish of the graded surface and inaccuracies in grade and slope. This is because backlash can produce blade tip movement. In a motor grader with the dimensions previously stated, a backlash of 0.22 inch produces 0.92 inch movement at the blade tip.
It appears that the special drive pinion of U.S. Pat. No. 3,911,758 probably reduces the backlash problem.
Another severe problem is that a motor grader blade is normally operated at an angle of approximately 45° from the longitudinal center line of the grader, either to the right or to the left. This causes wear to occur only on a very limited number of circle teeth, and only one tooth of the pinion and the circle mesh carries the entire load. This problem is somewhat obviated in U.S. Pat. No. 2,928,381 where there are two circle pinions engaged with the internal gear, so that wear is spread over more than 90° of the internal gear and two teeth are in engagement at all times. Nevertheless, this only alleviates the problem and may complicate backlash problems because of inherent differences in the backlash between the gear meshing at each of two drive pinions with one of the two meshes carrying the load when the blade force moves the circle to take out the backlash.
Further, the use of a pinion as a circle drive requires very accurate adjustment of the shoes which support the circle in order to maintain proper mesh between the drive pinion and the internal gear. The problem of adjusting the circle supporting shoes is complicated by the fact that the entire motor grader circle, grader blade, blade mounting and circle drive is at least coated with dust and may be caked with mud.
The present invention drives the circle internal gear by means of a barrel worm gear which either eliminates or greatly reduces the problems heretofore referred to.
Barrel worm gears employed with an internal gear are disclosed in U.S. Pat. Nos. 2,329,733 and 2,349,642. Hourglass gears, the reverse of a barrel gear, and used with externally toothed gears, are disclosed in such U.S. Pat. Nos. as 3,048,051, 3,386,305 and 3,710,640.
SUMMARY OF THE INVENTION
The principal object of the present invention is to provide a motor grader circle drive which eliminates or greatly reduces the problems that are inherent in a drive using a pinion as heretofore mentioned. The improved drive is achieved by the following structural features.
1. A barrel worm gear, or preferably two such worm gears set 60° apart, are used to drive the motor grader circle. The barrel worm gear has the same pitch diameter as does the internal gear with which it meshes.
2. The barrel worm gear is on an axis of rotation which is equal to the pitch angle of the helical worm tooth, thus permitting the barrel worm gear or gears to be used with an internal spur gear.
3. The problems and ill effects of backlash are minimized or eliminated by mounting the barrel worm gear for axial movement between a pair of belleville spring washers which center the barrel worm gear between abutments while permitting slight axial movement.
4. The barrel worm gear is made with a lead angle of approximately 5°, which automatically provides substantially complete circle braking action and prevents high forces imposed on the circle drive from entering the input gearing.
The improved structure produces a number of results in addition to eliminating or reducing the problems heretofore discussed. In the first place, tensile stresses are reduced approximately 65% because contact between the helical tooth and the internal gear teeth is always at the pitch line with full tooth contact, instead of there being what is essentially point contact as is true with a pinion drive. In addition, where two barrel worm gear drives are used the contact stresses are no more than about 10% of those experienced at the pinion-internal gear area of mesh.
This permits the barrel worm gear to be made from a much softer material than the steel used for the internal gear- for example, heat treated aluminum may be used; so that tooth wear is limited almost entirely to the relatively inexpensive and easily replaced barrel worm gear, and the life of the internal gear is greatly extended.
The braking force exerted by the barrel worm gear substantially eliminates transmittal of grading forces and impacts to the circle drive input, which permits these components to be of much lighter and less expensive construction than is required with the prior art.
The term "barrel worm gear" is used herein as a convenient, generally descriptive identification of the most significant element of the circle drive of this invention. The barrel worm gear is not a barrel gear in the same sense as that of U.S. Pat. No. 2,329,733, in which the gear surface is generated by rotating a segment of a circle of radius equal to that of the internal gear about an axis which is a chord of the circle defined by the internal gear.
The surface of the barrel worm gear here disclosed is generated by rotating an ellipse about an axis which is parallel to the major axis of the ellipse and in the plane of the ellipse. The result is a surface which gives the general visual impression of being barrel-shaped, but which is not a true barrel shape.
THE DRAWINGS
FIG. 1 is a side elevational view of a motor grader embodying the invention;
FIG. 2 is a perspective view of a sub-assembly consisting of a circle mounting bar, a circle, and a grader blade, in which the circle drive of the present invention is used;
FIG. 3 is a fragmentary, sectional view on an enlarged scale with parts broken away, taken substantially as indicated along the line III--III of FIG. 2;
FIG. 4 is a greatly enlarged fragmentary plan view of the barrel worm gear and the internal gear taken substantially as indicated along the line IV--IV of FIG. 3 with numerous parts omitted for clarity;
FIG. 5 is a fragmentary sectional view taken substantially as indicated along the line V--V of FIG. 3; and
FIG. 6 is a fragmentary sectional view taken substantially as indicated along the line VI--VI of FIG. 5.
DETAILED DESCRIPTION OF THE INVENTION
Referring first to FIG. 1 of the drawings, a motor grader, indicated generally at 10, includes a longitudinal main frame 11 the front end 11a of which is supported upon a dirigible front wheel assembly 12, and the rear end of which constitutes part of a traction chassis, indicated generally at 13, on which is mounted a power plant, indicated generally at 14. An operator's cab, indicated generally at 15, is on the rear portion of the main frame, forward of the traction chassis. A grader blade subassembly, indicated generally at 16, consists generally of a circle mounting bar, indicated generally at 17, which in the illustrated apparatus is a draw bar; a circle structure, indicated generally at 18; and a grader blade and blade mounting, indicated generally at 19.
The circle draw bar 17 is best seen in FIG. 2 to include a forward beam, indicated generally at 20, and a rearward circle carrying structure, indicated generally at 21, the forward part 22 of which is integral with the rear end of the beam 20. Behind the part 22 of the carrying structure said carrying portion has a section 23 the depth of which is great enough that it forms a housing extending below the circle 18. The housing section 23 receives a drive means sub-assembly, indicated generally at 24. The housing section 23 of the circle draw bar merges into a nearly semi-annular upright wall 25 which is part of an internal housing for the circle 18, and integral with the wall 25 is a horizontal top wall 26. An integral flange member 27 overlies the more inward portion of the circle.
The subassembly 16 is mounted under the main frame 11 by means of a front mounting element and rear mounting elements which engage with cooperating elements carried upon the main frame. At the front end 20a of the circle draw bar is a ball 28 which forms part of a ball and socket connection (not shown) by means of which the front of the circle draw bar is connected for universal movement on the front end 11a of the main frame. At the back end of the housing section 23 of the rearward circle draw bar portion 21 is a pair of aligned, laterally extending upright plates 29 which are provided with balls 30 that make ball and socket connections with fittings (not shown) on the lower ends of a pair of hydraulic cylinder and piston units 31 which are carried upon the main frame 11. Thus, operation of the hydraulic cylinder units 31 swings the circle draw bar 17 about the ball and socket connection including the ball 28, which in this respect provides a horizontal pivot axis. A ball 30a on one of the webs 29 provides for a ball and socket connection with a side-shift cylinder (not shown) which shifts the draw bar sideways, with the ball 28 providing a vertical pivot axis.
Referring now to FIG. 3, the housing 23 has a bottom plate 32 which is below the plane of the circle 18 and extends continuously around the circle carrying structure 21, the rearward portion of the bottom plate 32 being semi-annular in shape and welded along the lower margin of the semi-annular upright wall 25. The periphery of the bottom plate 32 is circular, and at its forward portion is an upstanding lip 33 which has an upright outer surface 34 and a shoulder 35 which receive a removable ring 36 that supports the circle 18. There is an antifriction wear strip 37 between the face 34 of the lip and the circle 18, and an antifriction wear strip 38 is also positioned between the ring 36 and the circle 18. A seal 39 in the face 34 and a seal 40 in the upper surface of the ring 36 prevent lubricant from leaking out of the chamber 23. Similar antifriction wear strips and seals are associated with the circle 18 and the ring 36 throughout their circumferences.
The laterally extending upright plates 29 close the rear of the housing 23 at its two sides, and a generally transverse, upright wall structure 41 connects the plates 29 to form the rear of the housing 23. An upright enclosing wall 42 connects at its rear end with the plates 29 outwardly of the rear housing wall 41, extending along both sides of the housing and having an arcuate forward portion 43 along the lower margin of which is an inwardly extending flange 44 which cooperates with the upright lip 33 to define a drive opening which is closed by the inward portion of the circle 18 and into which an integral internal spur gear 45 of the circle extends so that its teeth 46 may be engaged by a part of the drive means 24 as will be described.
Surmounting the housing 23 is a top plate 47 which is welded to the peripheral wall 42, the upright back wall 41 of the housing, and the upright transverse plates 29. The top plate 47 has two openings 48, one of which is seen in FIG. 3, and said openings accommodate the two drive means sub-assemblies 24.
Each of the drive means sub-assemblies 24 includes a circular mounting plate 49 which serves as a closure for one of the openings 48. The mounting plate has a pilot flange 49a surrounded by a seal 49b, and an indexing dowel 49c seats in a blind bore in the top plate 47. A circumferential array of machine screws 50 secure the plate 49 to the top plate 47.
Secured beneath the mounting plate 49 is a support, indicated generally at 51, which is seen in FIGS. 3, 5 and 6 to consist of a molded or a die cast frame which has end members 52 and 53 connected by a rear wall 54, and an arcuate bottom wall 55 with a pilot boss 55a that seats in a blind bore in the bottom plate 32. Formed integrally with the mounting plate 49 just inside the juncture of the walls 53 and 54 is a sleeve 56 which has upper and lower inturned flanges 57 and 58, respectively. Formed in the bottom 55 of the support in axial alignment with the sleeve 56 is a hollow boss 59. At the upper end of the sleeve 56, on the top surface of the mounting plate 49, is an annular boss 60 which serves as a support for a hydraulic motor 61 which has a splined output shaft 62 extending into the upper portion of the sleeve 56 above the upper flange 57. Removably mounted in the sleeve 56 is a bearing support tube 63 the upper end of which has an external flange 64 that overlies the upper internal flange 57, and small fastening screws 65 secure the tube 63 in the sleeve 56.
An upper antifriction bearing means 66 and a lower antifriction bearing means 67 are fixed in the tube 63, and a bearing ring 68 is seated in the annular boss 59; and a drive shaft 69 which has a splined slip connection 70 at its upper end is journalled in the bearings 66, 67 and 68, with its splined slip connection 70 in driving engagement with the hydraulic motor output shaft 62. On the drive shaft 69 is a drive worm gear 71.
Referring now to FIG. 5, a mounting spindle 72 is carried in hollow bosses 73 and 74 in the respective support side walls 52 and 53. The spindle 72 has a flange 75 which overlies the outer surface of the boss 73 and receives fastening screws 76; while the opposite end of the spindle 72 seats in the boss 74 and receives a removable fastening disc 77 and screws 78 which screw into tapped bores in the end of the spindle 72. Journalled on the spindle 72, by means which will be described, are a spiral input gear 79 which is in driving engagement with the worm drive gear 71, and a barrel worm gear, indicated generally at 80.
The mounting for the input gear 79 and the barrel worm gear 80 comprises a sleeve 81 which is journalled upon the spindle 72 on sleeve bearings 82; and the sleeve 81 has a fixed radial abutment 83 at one of its ends and a removable radial abutment 84 at its other end. Longitudinal keyways 85 in the sleeve 81 receive internal fingers of the abutment 84 and also receive keys on the spiral input gear 79 which has an outer end face 86 that is separated from the boss 74 by thrust bearings 87.
The barrel worm gear 80 has an axial bore 88 with an inset central portion 89 that defines outwardly facing shoulders 90, and in the two ends of the bore 88 abuting the shoulders are annular inserts 91. One end portion 92 of the barrel worm gear 80 surrounds the fixed radial abutment 83, and the opposite end portion of said barrel worm gear is spaced from the removable radial abutment 84. The barrel worm gear 80 with its annular inserts 91 is free to move axially upon the sleeve 81, and is biased to a center position between the abutments 83 and 84 by belleville springs 93 which have their inner margins bearing upon the inserts 91 and their outer margins bearing upon the abutments 83 and 84, respectively.
The barrel worm gear 80 has a helical tooth 94. The barrel worm gear 80 has its longitudinal surface 95 which is the base of the helical tooth 94 convexly curved; and said surface 95 is generated by rotating an ellipse about an axis which is parallel to the major axis of the ellipse and in the plane of the ellipse. The result is a surface which gives the general visual impression of being barrel-shaped, but which is not a true barrel shape. The pitch radius of the helical tooth 94 is the same as the pitch radius of the internal gear 45. Additionally, the barrel worm gear 80 has a lead angle of approximately 5°, and its axis of rotation provided by the axis of the fixed spindle 72 is set at said angle of approximately 5° to the plane of the internal gear 45 which makes it possible for the internal gear to be a simple spur gear. With the pitch radius of the helical tooth 94 the same as that of the internal gear 45, the helical tooth 94 has a wide area of surface engagement with the internal spur gear teeth 46, and during its rotation either one or two turns of the helical tooth 94 are engaged with the spur gear teeth 46. This, combined with the large area of contact between the helical tooth 94 and the teeth 46, affords very low bearing pressures between the helical tooth and the spur gear teeth.
Additionally, as seen in FIG. 2, there are two drive means sub-assemblies 24 each of which has a barrel worm gear 80 engaging internal gear teeth 46, so the driving load is divided between the two; and in addition the areas of engagement of the two barrel worm gears with the internal gear are 60° apart which spreads the wear on the internal gear teeth 46 over a substantially larger arc than is the case where only a single drive gear is used with the internal gear.
The greatly reduced forces at the engaging surfaces of the teeth makes it possible to fabricate the barrel worm gear 80 from a relatively soft material, such as heat treated aluminum, so that gear wear is almost entirely restricted to the relatively inexpensive and easily replaced barrel worm gear, leaving the expensive and hard to replace internal gear with very little tooth wear.
Each of the drive means 24 may be readily removed from the circle carrying structure 21 by removing the fastening screws 50 and lifting it out of the housing 23. There is no tooth interference at any position of the barrel worm gear 80, so each of the drive means 24 may be easily mounted in and removed from the housing 23.
The floating mount of the barrel worm gears 80 between the belleville springs 93 permits them to adjust to backlash, so that differences in backlash on the two barrel worm gears 80 at various times during the operation of the device are automatically compensated and the driving force is quite closely balanced between the two barrel worm gears 80 at all times.
The driving load exerted on the drive means support 51 is carried into the top plate 47 by the mounting plate 49 and the dowel 49c and screws 50, and is also carried into the bottom plate 32 by the pilot boss 55a, thus distributing the load about the housing 23.
Sealing of the housing 23 by the seals 39, 40 and 49b permits the housing to serve as a sealed lubricant chamber, so the drive gear 71, the input gear 79, and the barrel worm gear 80, as well as the internal gear teeth 46 where they engage with the helical tooth 94, are all operating in an oil bath.
The foregoing detailed description is given for clearness of understanding only and no unnecessary limitations should be understood therefrom as modifications will be obvious to those skilled in the art.
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A motor grader circle drive has an internal spur gear secured to the circle, and the internal gear is driven by one or two barrel worm gears, each of which in turn is driven from a hydraulic motor by an input worm and an input spiral gear keyed to the barrel worm gear, each barrel worm gear is journalled on a spindle in a support and is free to move endwise between a pair of radial flanges while being centered by a pair of belleville spring washers so as to compensate for backlash in each barrel worm gear and to permit substantially even distribution of driving force between the barrel worm gears when two are used. This structure operates at very low tooth pressures so as to permit the barrel worm gear to be made of a relatively soft material such as heat treated aluminum. The support, worm gear and input gears are made as a prefabricated sub-assembly, which is easily installed or removed; and using a soft material which wears much faster than the internal gear protects the latter from wear.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S. Provisional Application Ser. No. 60/661,280, filed Mar. 11, 2005, the disclosure of which is hereby incorporated by reference in its entirety.
BACKGROUND
[0002] 1. Field
[0003] This disclosure relates to software and more particularly to a system and method for assisting job seekers in their job search efforts.
[0004] 2. General Background
[0005] Various job search vehicles are available to a job searcher or recruiter today on the Internet, e.g. the World Wide Web (web). However, the available resources that can be scrutinized are somewhat limited. Accordingly there is a need for a system that more completely searches and organizes information that can be obtained from as many sources as possible via the Internet and present search results in an effective manner to a job searcher in response to a query.
SUMMARY
[0006] The system described herein is a system for improved job search that operates through the use of several techniques including scraping technology to scour the web and obtain job opportunity information from career sites available on the Internet, and particularly the World Wide Web, although, as job information may be distributed on other networks now known or to become known, the system and functionality described herein is applicable to any distributed information environment whereby information can be obtained by manual or automated systems.
[0007] A job seeker seeking information about jobs will have a larger universe of job information to review when utilizing the system described herein. Specifically, the system makes use of scraping technology, to build a database that is populated with job information data sets. The database may also include job information from other sources such as job information supplied by corporations seeking applicants and/or provided by methods other than through scraping. The system receives the job information and then, utilizing an internal quality management process, maximizes the quality of the information contained in each individual job information data set to maximize usefulness to the user and to improve the user's overall job searching experience when utilizing the system described herein.
[0008] This system includes a scraping module having one or more scraping engines operable to scrape job information data from job listings on the corporate career sites and job boards, wherein the scraping module receives and stores the scraped job information data set in a database. The system also has a scraping management process module coordinating operation of and communication between the scraping engines and the career sites and job boards. A scraped listing quality management process module is coupled to the scraping management process module analyzing selected scraped job information data sets stored in the database. A job categorization module examines and categorizes job information stored in the database into one or more of a predetermined set of categories and returns categorized job information sets to the database. An extractor module communicates with the database and compiles and transfers categorized job information data from the database to a search bank. The search bank is then accessible by a job searcher through a job search client server cluster connected to the Internet.
[0009] A preferred embodiment of the method of this disclosure includes operations of scraping job information data sets from one or more job listings on one or more corporate career sites or job boards, storing the scraped job information data corresponding to each scraped job listing in a database, analyzing each scraped job information data set stored in the database for conformance to predetermined quality criteria, categorizing each job information stored in the database into one or more predetermined job categories and returning the categorized job information data sets to the database, and transferring categorized job information data sets from the database to the search bank.
[0010] The categorizing operation preferably includes operations of comparing text of each scraped job information data set with previously categorized job information text in a categorization database, and determining a confidence value in each predetermined category for each scraped job information data set. More preferably, the method includes flagging each categorized scraped job information data set that has a confidence value below a predetermined value for manual review, and providing a manual review interface permitting a reviewer to verify any flagged categorizations.
[0011] The method further may include assigning a confidence value for the category assigned to each job information data set returned to the database and flagging any job information data set returned to the database having an assigned confidence level below a predetermined threshold. The techniques utilized in automatic categorization of a product, including such products as job listings, are described in detail in U.S. patent application Ser. No. 10/920,588, filed Aug. 17, 2004, and entitled Automatic Product Categorization, assigned to the assignee of this disclosure.
DRAWINGS
[0012] The above-mentioned features and objects of the present disclosure will become more apparent with reference to the following description taken in conjunction with the accompanying drawings wherein like reference numerals denote like elements and in which:
[0013] FIG. 1 is a block diagram of a system in accordance with an embodiment of the present disclosure.
[0014] FIG. 2 is an exemplary user (job seeker) search results interface for use in an embodiment of the exemplary system shown in FIG. 1 .
[0015] FIG. 3 is an exemplary user (job seeker) search input query interface for use in an embodiment of an exemplary system shown in FIG. 1 .
[0016] FIG. 4 is a simplified process flow through system shown in FIG. 1 .
[0017] FIG. 5 is a functional diagram of scraping in accordance with an embodiment of the present disclosure.
[0018] FIG. 6 is diagram of the job categorization control module in the embodiment of the system shown in FIG. 1 .
[0019] FIG. 7 is an operational flow diagram of the job categorization process in accordance with an embodiment of the system shown in FIG. 1 .
[0020] FIG. 8 is a screen shot of an exemplary document categorization platform service user interface for the job categorization process.
[0021] FIG. 9 is a process flow diagram for a job categorization manual review interface module.
[0022] FIG. 10 is a screen shot of an exemplary user interface for a job categorization manual review interface module.
[0023] FIG. 11 is a screenshot of an exemplary user interface of job information being manually reviewed.
DETAILED DESCRIPTION
[0024] An overall architecture diagram of the job search system 100 in accordance with an embodiment of this disclosure is shown in FIG. 1 . The system 100 can be thought of as having three sections: an external input section 101 , a data handling section 103 , and an output handling section 105 . Basically the data handling section reaches to the external input section 101 for job data, processes the data, organizes and verifies validity of the data, categorizes the job data, and provides the data to the output section which may be accessed eventually by a job seeker 107 via the internet 110 .
[0025] The external input section 101 includes the job postings that may be accessed by the data handling section from such sources as corporate and company career sites and a number of other job boards 102 . These corporate career sites and job boards 102 currently consist of several thousand company career sites. Also providing input to the data handling section 103 are systems operations personnel 104 , listing reviewers 106 and categorization experts 108 . These entities provide various input via an intranet 109 through suitable web browser interfaces such as Internet Explorer marketed by Microsoft Corporation utilizing administrator user interfaces appropriate to their purpose.
[0026] The data handling section 103 comprises a series of modules that together assimilate job information scraped from the sites 102 into an orderly configuration generally described as follows. A scraping module 112 in the data handling section 103 has one or more job scraping engines 114 . These job scraping engines are software routines that are used to query each of the several thousand sites and job boards 102 for new job postings and job information data sets. Such job information data sets include parameters unique to the job posting such as title, company, city, state, salary, hours, skills, qualifications, experience etc. and a detailed job description that describes, in paragraph form, the duties, experience and tasks to be performed in the job. The scraping module 112 comprises one more scraping engine farms 114 that typically use different scraping technologies and methodologies which may be developed as a matter of design choice but are preferably specifically directed in a preferred embodiment herein for searching over a global electronic network such as the Internet 110 , with each engine 114 being optimized for either a particular type of scraping task or particular type or set of corporate sites. For example, the Kelkoo scraping engine farm, developed by Kelkoo, Inc. in Europe, now a subsidiary of Yahoo, Inc., is optimized to thoroughly scour a predetermined known corporate site or listing site. The Kelkoo scraping engine is optimized to follow internal links within the site to specific internal locations to extract job information data sets. However, it does not follow external links. The Café/Kelsa Scraping engine farm, developed by Yahoo, Inc., and described in U.S. patent application Ser. No. 11/064,278, filed Feb. 22, 2005 and entitled Techniques for Crawling Dynamic Web Content, is optimized to systematically examine a seed URL and follow every link within the site and follow every internal and external link that may be provided on that URL as well as links it finds on its “crawl.”
[0027] Preferably, a scraping agent is created for each career site 102 that is desired to be searched for job postings/listings and corresponding job information. The scraping agent uniquely has a URL address for its particular destination site, and essentially is a file that provides the parameters to the Kelkoo scraping farm as to what areas on a particular site can be searched, how often, and when for each particular site so that the individual sites are not overused and overscraped. In contrast, the scraping agent for the Cafe Kelsa scraping engine farm preferably simply contains the site URL and scraping frequency requirement information.
[0028] Once the scraping module 112 performs a scrape of the desired career sites, the results of the scraping exercise are passed to a scraping management process module 118 and stored in a Raw Database 122 . This scraping management process module 118 performs functions such as scrape scheduling, error handling, recovery in the event of software failures, error logging and reporting, and monitoring of the scraping process. Thus, for example, scraping management process module 118 may perform objective tests against the raw data to identify gross errors such as non-delivery of information from a site designed to be scraped, garbled data, or data that is comprised of fewer than a predetermined number of bytes, which would be indicative of a failed scraping exercise. Scraping management module 118 is administratively operated externally by operators 120 via an internet 110 connection into the module 118 in a known manner. The resulting output of the scraping management module 112 is fed back to and updates the raw database 122 . This database 122 contains the raw data as received by the scraping process performed by the scraping module 112 , and as corrected in the scraping management module 118 . The output of module 118 is also collected in a cooked, i.e. modified, database 126 .
[0029] The scraping management process module 118 communicates with the scrape listing quality manager module 124 . The scrape listing quality management module 124 instructs the scraping management process module 118 when to transfer a job information data set to the cooked database 126 and then this module 124 preferably begins examination of that data set. The scraped listing quality management module 124 pulls scraped data from the cooked database 126 and performs further quality management tests on the scraped job information received as part of the scraping exercise in module 112 . For example, the listing quality management module 124 performs a high level of quality management such as collecting byte count or job count information from the scraping exercise, performs site comparisons, checks for required fields, compares with previously encountered listings from the same job site to compare data formatting and also to delete duplicates, i.e. “de-dupe,” data to avoid redundant listings. This module also detects and removes dead links and filters profanity and offensive text. The scrape listing quality management module 124 then updates the data set and returns it to the cooked database 126 . Again, this module 124 is administered and operated by operations via an intra 109 connection via a suitable web browser.
[0030] If, in examining a job information data set in module 124 , it is determined that the quality does not meet predetermined criteria, for example, a manual review quality flag can be set in that data set when it is returned to the cooked database 126 by the listing quality management module 124 . A scrape listing quality manual review interface module 128 permits an operator to periodically examine the cooked database 126 for data sets having these set flags. This module 128 indexes these data sets and then utilizes the services of human listing reviewers 130 to perform the highest level of quality management on the scraped job listings to ensure the highest level of quality or to review listings that automated modules 118 and 124 were unable to pass as quality listings.
[0031] Depending on the nature and scope of the quality issues presented by a particular listing, the job listing (job information data set) may be passed to the cooked database 126 through the scraped listing quality management module 124 . This cooked database 126 contains job listings that have undergone a satisfactory level of quality management. Thus, modules 118 and 124 all have the ability to pass approved job listing data sets to the cooked database 126 as well as job listings that have been manually reviewed as part of the manual review process module 128 .
[0032] A job categorization control process module 132 then reviews the job information data sets that pass the quality reviews in the cooked database 126 in order to accurately categorize each job listing. It is important that a job listing be placed in the proper job category, such as for example, information technology, healthcare, accounting, etc. The job categorization control process module 132 preferably is automated.
[0033] In addition, a manual review interface module 134 is available to review job information data sets that the module 132 flags for manual review. This module permits categorization experts 136 to verify categorization data via an intranet connection 109 and update content of a manual categorization “mancat” database 138 and the DCP service 140 . However, the function of the experts 136 may alternatively, as is the case with listing reviewer entities discussed earlier, be automated routines in the future as such systems become more sophisticated.
[0034] The job categorization control process module 132 is preferably automated, while the manual review process module 134 provides a manual check on quality, thus providing a high degree of accuracy in job categorization. The results of this categorization process are stored in “mancat” database 138 , which is a contraction name for the manual categorization database.
[0035] The job categorization process module 132 and the manual review interface 134 both feed job categorization information to a document categorization platform (DCP) service module 140 , identified herein as DCP 140 . The DCP service module 140 looks at the jobs and analyzes the entire text of each job description in each job information data set for comparison to a database of other text to determine a confidence value. Thus, the DCP service module 140 is an automated process that, over a time period, can be “trained” to accurately characterize job information data sets scraped and passed through various levels of quality management.
[0036] The DCP service module 140 functionality is described in more detail in U.S. patent application Ser. No. 10/920,588, mentioned above, along with the related U.S. patent applications referred to therein. The DCP service module 140 preferably compares the text of a newly submitted job description with existing job information data sets in the same category, and look for specific characteristics such as education, use of similar terminology, length, companies worked for, etc., to arrive at a particular level of confidence that the categorization is accurate. Failure to achieve a particular level of confidence through this text matching, for example, a 70% match or less would result in job information being held and placed into the manual characterization database 138 for manual review. A 90% match, would result in job information having a high degree of confidence. This information is attached, or otherwise associated with job information that is stored in the cooked database 126 . Similarly, a job description that has been manually characterized can be identified to cooked database 126 as a job description with a high degree of confidence that has been correctly characterized or categorized.
[0037] For archival storage purposes, periodically the contents of the cooked database 126 are placed in the archive database 142 . Similarly the content of the other databases 138 and 122 may be periodically rotated and dumped for archival purposes to the database 142 .
[0038] Another component in the data handling section 103 is an extractor module 144 . This extractor module 144 works in conjunction with and interfaces directly to a scraped job search bank 146 in the output section 105 of the system 100 . The extractor component or module 144 takes cleansed and categorized job information data sets from the cooked database 126 . It reformats them into a format for use by the scraped search bank 146 and transfers the reformatted data sets to the search bank 146 .
[0039] The server cluster 148 , for example, in reaction to search terms provided by a job seeker 107 through the Internet 110 , accesses the search bank 146 , searches the database 126 , and passes identified scraped job search listings to the cluster 148 and then to a job seeker 107 through the Internet 110 for depiction on a search result user interface screen such as is shown in FIG. 2 . The extractor module 144 preferably also periodically queries the cooked database 126 to provide new scraped job postings to the scraped search bank 146 so that this scraped search bank 146 maintains a current bank of listing data sets.
[0040] The data output section 105 comprises the job search web server/client cluster 148 and a number of data source modules to this cluster 148 . The scraped search bank 146 is one of these. An ad system premium listing module 150 , a paid search bank 152 , an overture system content match module 154 and a link builder module 156 are queried by the job search web server/client cluster 148 .
[0041] The ad system premium listing module 150 organizes and provides the cluster 148 with advertisements from specific employers or recruiters that have a paid premium account with the host of the system 100 . These premium advertisements may be displayed to the job seeker in a special box, bannered, highlighted, or otherwise set off from the other listings that may be presented to a job seeker 107 in response to a particular search request.
[0042] The paid search bank module 152 is a special search bank for which an employer member 160 may access upon a fee payment to the host of the system 100 . This paid search bank module 152 identifies, stores, and tracks job listings from those job recruiter employer or corporations who pay a fee to ensure that their posted job listings receive a higher or emphasized placement on a user interface presented to the job seeker 107 . Thus the paid postings are provided directly into the search bank 152 by the member company via a member desktop 162 or gateway 164 . Paid search bank 152 contains information provided by job listing entities that have paid a premium to the operator of the system 100 described herein to push listings in connection with certain desired search categories provided by a user, so that such search results are provided in a prominent position to the user via the user interface 200 in exchange for a premium payment.
[0043] The Overture system content match module 154 queries whether there are any advertisements that match the job searcher's search criteria. These advertisements are previously stored in or linked to a paid database for use by the host of the system 100 . Examples of such advertisements are shown in the search results user interface screen shot shown in FIG. 3 .
[0044] The link builder module 156 provides linkage cookies and addresses to link to other sources of jobs that match the search terms provided by the job seeker 107 . In some instances, in order for a job description to be viewed, the job seeker must be passed to a particular website to see the listing. In such circumstances the site might require a particular security element such as cookie, password etc. before the job information may be viewed. Accordingly, link builder module 156 provides the necessary interface characteristics in the case where a site needs a particular cookie or other identifier. The link builder module 156 manages the process to build a URL which includes the necessary information required by the site such as for example, a session cookie to access the job listing. The result of the link builder module 156 may be provided to the job seeker 107 in addition to the particular jobs of interest from his/her search request.
[0045] With continued reference to FIG. 1 , the web server cluster 148 acts as a gateway interface to a job seeker 107 seeking to utilize the system 100 described herein. The job seeker 107 , in order to initiate a search request on the system 100 , is preferably presented with a user interface similar to that shown in FIG. 3 . The cluster 148 then searches to obtain information from the system search banks 152 , 154 , 146 and 150 and presents it in an easy to use and efficient manner to the querying job seeker 107 such as in the exemplary results interface shown in FIG. 2 .
[0046] A job seeker 107 entering a search request 302 into a user interface 300 such as that depicted in FIG. 3 interfaces with the server cluster 148 , which in turn presents an aggregated result to the job seeker 107 as shown in FIG. 2 . Thus the user would see, as described below, premium listings through the provision of listings identified by the ad system premium listing module 150 , job search bank 152 , the banks 154 , 150 , 146 and crawled jobs from bank 156 .
[0047] Turning now to FIG. 2 , an exemplary screen shot of a user query result interface 200 is shown. This user interface 200 gives the job seeker an opportunity to review all of the job information that match his query. In addition, it permits the job seeker to submit a different or more refined query. Display portion 202 gives the user an opportunity to review all of the job information that would match a particular search criteria, for example, in FIG. 2 , a software developer position in Illinois. The job seeker may review all of the job information available as a result of the search for software developer positions, or may review only those descriptions that have been updated in the past 24 hours, 7 days, or other preselected time period. Also the job seeker may structure his or her search by experience level, location, or other characteristic or subcategories within a job description.
[0048] The interface 200 also displays result segments separated by multiple preferable result groupings. Thus the system 100 may present a segment for premium listings 204 obtained from ad system premium listing module 150 , which permits the host of the system 100 to utilize the system 100 as a revenue enhancing tool by providing the opportunity for business seeking employers to pay premium to have their job listings obtain a more prominent position in the result portion of the user interface 200 presented to the job seeker 107 .
[0049] The user interface 200 also preferably includes a second subsection 206 which presents results of the search from the paid job search bank 152 . A third subsection 208 presents non-premium algorithmic search results which is a direct result of searching the scraped search bank 146 . A fourth section 210 provides more general paid links from the overture system content match module 154 . Finally, a number of advertisements 209 may be displayed from a search of the ad system premium listing module 150 .
[0050] With reference to FIG. 4 , a simplified functional flow diagram 400 of the scraping performed by the system 100 is shown. This scraping process begins at operation 402 where career sites 102 are scraped. Control then passes to operation 402 where the scraped listings are fed to storage in the raw database 122 . Once stored, control passes to operation 404 . In operation 404 , the scraped listings are submitted to quality assurance/quality management processes described above and further herein with reference to modules 124 and 128 . Control then passes to operation 406 . In operation 406 the clean scraped listings are fed into storage in cooked database 126 . Control then passes to operation 408 . Here the clean scraped listings are categorized in modules 132 and 134 . Control then passes to operation 410 . In operation 410 the clean and categorized scraped listings are fed to storage again in the cooked database 126 . Control then passes to operation 412 . In operation 412 , the cleaned and categorized scraped listings are indexed and formatted in the extractor module 144 for use by the semi-structured search engine described herein. Control then passes to operation 414 . In operation 414 the indexed listings are stored and compiled in the scraped search bank 146 for use. Control then passes to return operation 416 .
[0051] Scraping involves the following components 500 shown in FIG. 5 : the Kelkoo “Sniffer” and Café/Kelsa crawlers in scraping engine 114 , a series of Agents 502 to scrape web sites 102 for jobs, preferably a MySQL database such as raw database 122 to store the scraped jobs and agent logs, and Runner scripts 504 to launch the agents 502 .
[0052] The following is a summary of how data flows preferably through the scraping farm 112 in the system 100 . At the beginning of the scraping cycle the “job_current” table 500 is truncated and its contents are copied to an archive table (not shown). Archives of scraped jobs are preferably stored for a limited period only (e.g. 7 days).
[0053] The Kelkoo “Sniffer” in the scraping engine 114 is a Java program that is used to launch adapters (a.k.a. agents 502 ). The scraping engines 114 scrape the job boards 102 , via the Agents 502 . Each agent 502 preferably consists of three text files: agent.info, agent.props, and agent.sql. A single agent is used to scrape a single web site. The agent files are stored in an agent specific directory. Then the agents 502 dump the scraped job information sets into a “job” table (note that there can be several job tables) 506 , two of which are shown in FIG. 5 . The Runners 504 copy the job information sets, or records, from the “job” table(s) 506 to the “job_current” table 510 . Components downstream from the runner 504 , such as the Quality Manager module 124 and the Categorizer modules 132 and 134 pull copies of the job records from the cooked database 126 and perform quality management and categorization operations on the records in the job_current table 510 , which is preferably part of the cooked database 126 . The results are then passed back to the cooked database 126 shown in FIG. 1 .
[0054] The Kelkoo Sniffer search engine 114 thinks about agents 502 as virtual SQL tables. The schema of the virtual table is defined in the agent.sql file. The agent.info file is a SELECT statement against the virtual table that the Sniffer search engine 114 runs. The agent.props file contains the scraping logic that is used to fill the virtual table. The scraping logic is a sequence of steps that are carried out by various filters. Filters are Java classes that make up an Adapter Development Kit (ADK). Filters are executed sequentially and can read and write variables to a common context. There are filters to: find a string or a pattern in an html page and save it, manipulate variables of the context, loop over a re-occurring pattern and execute other filters in a loop, go to a page identified by a URL and retrieve its content, etc.
[0055] The output of an agent 502 is a text file that contains SQL INSERT statements for each scraped job. The Sniffer search engine 114 uses this data file to load the scraped job information data sets or records into a MySQL table, called “job” (the actual table name is a configuration parameter) 506 . The Sniffer 114 is configured via various command line parameters and an arbitrary number of property files that are passed in on the command line. The most important configuration parameters of the Sniffer search engine 114 are: Name of the MySQL database, database user and password, name of the table to dump the scraped records to; and the Path to the agent request files and the directory that contains the agents 502 .
[0056] The Sniffer search engine 114 is preferably single threaded: it loads and runs one agent 502 at a time. After running an agent 502 the Sniffer search engine 114 inserts a record to the “report” table 508 with information about: the time of the run, the name and path of the agent 502 , the number of scraped records (jobs), and possible errors.
[0057] The agent files are stored in a CVS repository. The version of the agent 502 that has passed QA is tagged with a special CVS tag. This scheme allows agent developers, testers and the production system to work on the same tree, yet to avoid running un-tested agents in production.
[0058] The agent runner 504 is a Perl script that is developed for the system 100 . The Runner 504 requires that the agent files be available on the local file system. Before the Runner 504 is started the local CVS tree is synced to the production tag to download all the agent files that should be run.
[0059] The runner 504 performs the following steps:
1. It reads its configuration file. This contains the list of agents 502 to run. Each Runner has an id that is passed in as part of the configuration. 2. It generates configuration files for the Sniffer 114 based on its own configuration. 3. It deletes all the records from the job_current table 510 that belong to the agents 502 to be run (this in most cases is unnecessary, since preferably the job_current table is truncated every day). 4. It launches the Sniffer search engine 114 that runs the agents 502 . 5. It preferably processes each record in the job table to strip the job information from html tags. Each Runner has its “own” job table 506 whose name is generated using the runner's id (e.g. “job1”). 6. It dumps all the records from the job table 506 to the job_current table 500 . The job records contain the id of the Runner, which helps downstream components to easily identify records that came from a particular Runner 504 . 7. It writes a summary of the agents run to its log file. This information is retrieved via queries to the job, job-current and the report tables 506 , 500 and 508 respectively. 8. Finally, it invokes the Quality Manager management process module 124 via a secure shell such as SSH, so it can execute on a separate machine. The ID of the Runner 504 is passed to the Quality Manager module 124 , so it knows which records to process from the job_current table 500 .
[0068] The system 100 is primarily designed to handle scraped jobs in addition to listings provided from standard sources that generally have standardized formats and categorizations. These scraped jobs typically may not have category assignments such as Accounting, Banking, Engineering, medical, dental, etc. In order to support a “browse by category” feature that jobseekers are most familiar with, we could have many human categorizers spend a great deal of time to manually classify jobs as they are scraped. However, this has substantial drawbacks. It is a very time consuming process. By the time the jobs are manually classified, they may be outdated already. Such a process requires a lot of human resources. Further different categorizers may not categorize in the same consistent manner. For this reason, an exemplary automatic Job Categorization System 600 that may be used is shown in FIG. 6 . This system 600 is capable of categorizing a job in a fraction of a second. It is substantially faster than human categorizer, and, it is consistent.
[0069] This Job Categorization System 600 contains several modules. A job categorization (Job Cat) Service module 602 which carries out the actual categorization routine. The Job Categorization Control Process module 132 is one example, which is described with FIG. 1 , which manages communication between the Job_current table 510 in the cooked database 126 , the ManCat database 138 , and the DCP 140 . The DCP 140 corresponds to one example of a Job Cat Service module 602 . The Categorization Training Process, which is used to enhance or maintain the accuracy level of the Job Cat Service 602 . This categorization training process involves the use of the job categorization manual review interface 134 and categorization experts 136 shown in FIG. 1 .
[0070] As described above, the jobs scraped are added to a MySQL job_current table 510 . Then the Job Categorization Process 600 will take each job from the job_current table 510 , and send it through the job categorization control process module 132 to the Job Cat Service module 602 to get a category and confidence assignment. Then the scraped job is sent back to the categorization control process module 132 and returned to the job_current table 510 . However, if a job falls below a predetermined confidence threshold it will be flagged, i.e. a flag set, and when it passes through the categorization control process module 132 a copy is also sent to the mancat database 138 for manual review via the manual review interface module 134 . The results of the manual review process performed in review module 134 are then used by the Categorization Training Process 606 to tune a new Job Cat Service value to replace the old one. The result of classification is written back to job_current table 510 and sometimes the mancat table 138 . The Manual review module 134 provides a UI to review both jobs in job_current and mancat tables.
[0071] FIG. 7 is an operational flow diagram of an implementation of the job categorization process 600 . The process begins in operation 702 when a sequence of job scrapings has been performed. Control transfers to operation 704 . In operation 704 the job attributes for the next job are retrieved from the job_current table 510 and the job information is properly formatted. The job attributes are then transferred to the job cat service 602 to find a proper category. Control then transfers to operation 706 where the job category and confidence level for that categorization are paired with the job. Control then transfers to query operation 708 .
[0072] Query operation 708 asks whether there is a matching URL existing in the mancat table for the latest particular job information. If there is, then control transfers to operation 710 . If not, the job is a new job, and control transfers to operation 716 .
[0073] In operation 710 , a string compare routine is performed on the last job with the same URL. Control then transfers to query operation 712 . Query operation 712 asks whether the listing in the mancat table 138 is the same as the current job being examined. If the job string compare is equal, then the answer is yes, and control transfers to operation 714 since it appears that the job is the same job. On the other hand, if the answer is no, the job is new, and control again transfers to operation 716 .
[0074] Query operation 714 asks whether the dcp_cat matches the man_cat of the latest job with the same URL. If the answer is yes, then the man_cat and dcp_cat are set equal and the dcp_cat confidence is set equal to 1.
[0075] The job parameters back to the job_current table 510 , and control transfers to query operation 718 . Query operation 718 asks whether there are more scraped jobs in the job_current table to be categorized. If not, control transfers to return operation 720 . If there are more scraped jobs to be categorized, control passes back to operation 704 and the job parameters for the next job are retrieved and formatted.
[0076] Returning to query operation 708 , if the URL does not exist in the mancat table, then control transfers to operation 716 . In operation 716 , the Dcp_cat and dcp_confidence are set, the confidence value is checked against the threshold that has been predetermined, and if the threshold is greater than the confidence value, the review_flag is set equal to 1. The job parameters are then passed to the job_current table 510 and again, control passes to query operation 718 .
[0077] Returning to query operation 714 , if the current jog has a URL in the mancat table 510 , the job is the same as the last job with the same URL, but the dcp_cat and an_cat of the latest job do not match, then something may be wrong or missing, and the job parameters are passed to both operations 724 and 726 . Operation 724 sets the dcp_cat, the dcp_confidence values, sets the expert_review flag=1 and feeds this data to the Job_current table 510 . Operation 726 sets the expert_review flag=1 and sends a copy of this job's parameters to the mancat database 138 so that manual review will be performed. In parallel, control again passes to the query operation 718 as described above.
[0078] Thus, for each job, the Job Categorization Control Process take job attributes from the job_current table, formats them, and sends them over to Job Cat Service managed by a well known public domain routine called Apache, method=POST), gets back a category and confidence score, goes through a chain of decision questions, and writes results back to the tables.
[0079] The Job Cat Service 602 also provides a web UI that allows administrators and system operators in a job (at least the job description) and submit the job to the Job Cat Service for categorization separately from the normal operation of the system 100 . Such an exemplary user interface 800 is shown in FIG. 8 .
[0080] The Job Cat Service 602 depends on Apache, a well known management routine to manage the training process 606 shown in FIG. 6 . The JobCat Service 602 contains a binary package that is a shared library of PHP extensions and also includes a Categorization library. Building the Job Cat Service 602 first requires a set of basic definitions i.e. a taxonomy 608 , of job categories and associated unique ID numbers. An exemplary set is shown in Table 1 below.
TABLE 1 Cat_id Cat_name 1 Accounting_Finance 2 Advertising_Public_Relations 3 Arts_Entertainment_Publishing 4 Banking_Mortgage 5 Clerical_Administrative 6 Construction_Facilities 7 Customer_Service 8 Education_Training 9 Engineering_Architecture 10 Government 11 Health_Care 12 Hospitality_Travel 13 Human_Resources 14 Insurance 15 Internet_New_Media 16 Law_Enforcement_Security 17 Legal 18 Management_Consulting 19 Manufacturing_Operations 20 Marketing 21 Non_Profit_Volunteer 22 Pharmaceutical_Biotech 23 Real_Estate 24 Restaurant_Food_Service 25 Retail 26 Sales 27 Technology 28 Telecommunications 29 Transportation_Logistics 30 Work_At_Home
[0081] An exemplary table of training job information, training data 610 , is associated with each of the categories in Table 1. This set of descriptions, plus the content of the mancat database 138 , is used to teach the Service to recognize classifications from the provided job information parameters that are preclassified. An example of this table is shown in Table 2 below.
TABLE 2 Field Type Null Comment Pindex Varchar(11) No, Primary key Title Varchar(11) Yes Ldesc Text No Mancat Varchar(101) No Actually set to the first industry setting initially Gid Int Yes Group id, some id are used by HJ internal for testing, they should not be used for training Hiretype Varchar(21) Yes Companyname Varchar(101) Yes Salarytype Varchar(21) Yes Sdesc Varchar(101) Yes Sourcetype Varchar(11) Yes Source Varchar(21) Yes Duration Varchar(3) Yes Position Varchar(21) Yes Experience level Degrees Varchar(31) Yes Salaryfrom Float Yes Salaryto Float Yes Ownerid Varchar(11) Yes Creatorid Varchar(11) Yes Editorid Varchar(11) Yes Ctime Date Yes Date created Mtime Date Yes Date modified Score Int Yes The YSS score, not used
[0082] For new training sessions, it is preferable to use both jobs from this table and those in the mancat table. As more and more manual reviewed jobs become available, it is preferable to eventually drop the original training set from the HotJob's read-only database.
[0083] In a preferred embodiment the columns of this table 2 and the mancat table are different, and this difference will remain, and the script that creates the training file will do all necessary mappings. The training process 606 consists of several PEARL scripts. A “create-training-file.pl” script takes jobs from both the mancat table 138 and a train data table 610 , and writes out a file containing all jobs in a DCP accepted format to generate the merged training data 612 . A “train-hj-dcp.pl” script is used to tune a few of the most useful parameters for classification. Each of the configurations specified will leave an output directory containing all the parameters that are needed to build a Job Cat Service data package, and a log file. A “parse-training-log.pl” script reads each of the log files generated by the train-hj-dcp.pl script and generates a report on accuracy for each configuration. An “archive-training-results.pl” script is used to archive the training results for that configuration after a configuration is used for deployment.
[0084] The training process 614 is basically a manual process that draws from the training data 612 , the taxonomy 608 , and sets of rules and schema 616 . Various dictionaries and tuning parameters 618 may also be utilized. The results involve optimization of new classifier parameters 620 with the results being provided into the job categorization service 602 as shown in FIG. 6 . Since the training process 614 is mostly manual, it is preferable to train on a few parameters, manually check the results, e.g. detail pages of classification, term weights, etc, and change some of the rules and dictionaries by hand, and repeat the process with different configurations in order to find the optimal settings for deployment. When such an optimal configuration is achieved, the new classifier parameters 620 are passed to the Job Categorization Service 602 . Once the Job Categorization Service is built up and running, scraped jobs can then be processed as described above.
[0085] The screen shot of the exemplary user interface 800 is presented to an administrator, operator or categorization expert 136 through the internet 110 using a web browser. The interface 800 provides three different modes 802 via a pull down menu as shown. The “all categories” mode lists all categories and their corresponding confidence values, sorted in descending order by confidence. The “Detail Statistics” mode shows the details on why a particular category is chosen. This mode is useful for an operator who tunes the system 100 . The “Best Category” mode shows only the top category for the job and its confidence. This is equal to the first result shown in “All Categories” mode, except here we show the category ID number, not a string. This mode is intended for automatic classification of jobs in the database, where the category ID number is preferred over the category name.
[0086] An operational flow diagram of the job categorization manual review process 900 that takes place in the job categorization manual review module 134 is shown in FIG. 9 . Operational flow begins when an administrative operator or a categorization expert 136 logs in via backyard in operation 902 . When the administrator logs in, he or she is presented in operation 904 with a user interface 1000 as shown in FIG. 10 . This user interface 1000 permits the administrator or expert reviewer choices of job category 1002 , company 1004 , and selection of a type of review 1006 to conduct. Control then transfers to operation 906 . In operation 906 , a first/next job information is retrieved from the mancat database 138 or the job-current file 510 in the cooked database 126 , depending on the administrator's prior selections in operation 904 . The administrator is presented with a user interface such as the exemplary interface 1100 shown in FIG. 11 .
[0087] This user interface 1100 displays the first/next job information 1102 along with the category confidence level s determined for each category. In this example, the job is a post-doc position at IBM Corp. The confidence levels are zero for all but Engineering_Architecture and Pharmaceutical_Biotech, and none of the levels match 100%. This position has been categorized as Engineering Architecture, but the confidence level is only 0.657, so it was flagged for manual review.
[0088] Referring back to FIG. 9 , when the job information is retrieved in operation 906 , control transfers to operation 908 where the administrator analyzes the categorization based on the full job information. The administrator then has three choices of action. First, he can invalidate the job in query operation 910 . Second, he can get more job details in query operation 912 by clicking on the job URL 1110 to enhance his review. Third, he can update a category definition or insert a new category in query operation 914 . If his decision is to invalidate the job in query operation 910 , then control transfers to operation 916 where the job is removed from the database 126 and from the mancat database 138 . Control then transfers to query operation 918 . Query operation 918 asks whether there is another job information in the queue of the mancat database 138 or job_current table 510 that has its expert_review flag=1 set. If so, control transfers back to operation 906 where the next job is retrieved for review.
[0089] However, if the decision in operation 910 is not to invalidate the job, control resets the expert_review flag=0, returns the job to the job_current table 510 and control transfers to query operation 918 . If the choice in operation 908 is to get more job details, control transfers to operation 920 , where the details are retrieved and control transfers back again to operation 908 . If the administrator then chooses not to get more details, the job listing record is again returned to the job_current table 510 after resetting the expert_review flag=0 and control passes again to query operation 918 . If the choice in operation 908 is to update the category in query operation 914 , then control passes to operation 922 .
[0090] In operation 922 the category of the job listing is changed or a new one added, and saved. The expert_review flag is set=0 and the job listing information is then transferred to the job_current database 510 and control transfers to query operation 918 . If there are no more job listings with expert_review flags set=1, control transfers to return operation 924 and the review session is complete.
[0091] Although functional components, modules, software elements, hardware elements, and features and functions described herein may be depicted or described as being fixed in software or hardware or otherwise, it will be recognized by persons of skill in the art that the features and functions described herein may be implemented in various software, hardware and/or firmware combinations and that the functions described herein may be distributed into various components or subcomponents on the network and are not fixed to any one particular component as described herein. Thus the databases described may be separated, unified, federated, or otherwise structured to best suit the preferences of the implementer of the features and functions described herein. Also, the functions described herein as preferably being performed manually may be performed manually or may be divided into subtasks which may be automated and ultimately performed by intelligent subsystems which mimic human operator interaction such as artificial intelligence systems which may be trained by human operations and ultimately function autonomously. Further features, functions, and technical specifications are found in the attached descriptions further below as well as the figures contained therein.
[0092] While the apparatus and method have been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the disclosure need not be limited to the disclosed embodiments. It is intended to cover various modifications and similar arrangements included within the spirit and scope of the claims, the scope of which should be accorded the broadest interpretation so as to encompass all such modifications and similar structures. The present disclosure includes any and all embodiments of the following claims.
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A computer system and method for capture and handling job listings obtained from various often unrelated corporate and job board postings via the internet for examination by a job searcher. This system includes a scraping module having one or more scraping engines operable to scrape job information data set from job listings on the corporate career sites and job boards, wherein the scraping module receives and stores the scraped job information data set in a database. The system also has a scraping management interface module coordinating operation of and communication between the scraping engines and the career sites and job boards, a scraped listing quality management module coupled to the scraping management interface module analyzing selected scraped job information data stored in the database, and a job categorization module that examines and categorizes each job information stored in the database into one or more of a predetermined set of categories and returns categorized job information to the database, and an extractor module communicating with the database for compiling and transferring categorized job information data from the database to a search bank. The search bank is then accessible by a job searcher through a job search client server cluster connected to the Internet.
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FIELD OF THE INVENTION
This invention relates to waste water treatment systems particularly adapted for the high temperature hydrolysis of cyanides in the waste waters.
BACKGROUND OF THE INVENTION
Cyanides are used in a variety of industrial applications, such as in the art of electroplating, steel heat treating and mining. In these processes, however, the waste solutions contain cyanide which presents a significant environmental hazard. Strict governmental regulations are in place which control the release of cyanides. This has necessitated the development of various processes to remove cyanides from waste waters. One example of treating cyanides is by alkaline chlorination. Chlorine and sodium hydroxide may be used to oxidize the cyanide to cyanates and subsequently to carbon dioxide and water. The problem with the alkaline chlorination process is that:
(1) chemical consumption increases with cyanide content in the waste waters; hence significantly increasing operating costs;
(2) the process does not destroy iron and other complex cyanides and hence dilution must be relied upon to comply with regulations;
(3) very careful control of the reaction is required; otherwise toxic cyanogen chloride can be released.
Another technique for removing cyanide from waste waters is by way of hydrolysis. At high temperatures and pressures, the following reaction proceeds rather quickly:
CN.sup.- +2 H.sub.2 O→HCOO.sup.- +NH.sub.3
An example of such hydrolysis is disclosed in U.S. Pat. No. 4,042,502. This patent discloses the use of a heat exchanger which has first and second flow paths where the second flow path is in heat exchange contact with fresh cyanide solution which is introduced to the heat exchanger through the first flow path. For the system to function, there is a continuous effluent flow to ensure constant heat exchange with continuous inflow of waste waters to be treated. Preferably, laminar flow is maintained within the heat exchanger which also constitutes the reactor. By way of heating the incoming waste waters in a preheater to a temperature of more than half the temperature reached in the heat exchange reactor, the system provides for continuous reaction within the heat exchanger. However, it is appreciated that with cyanide hydrolysis reactions, solids are generated as the cyanides are destroyed creating a build-up of sludge which presents a significant problem in having the reaction carried out within the heat exchanger due to flow of the effluent through valves and the like in which sludge can build up and detract from the overall efficiency of the hydrolysis reaction in the heat exchanger.
SUMMARY OF THE INVENTION
In accordance with an aspect of the invention, a waste water treatment system for high temperature hydrolysis of cyanide in a waste water stream has a reactor operating at a sufficiently high temperature and pressure to effect hydrolysis of any cyanide in a waste water stream introduced to the reactor. A heat exchanger system is provided, through which effluent from the reactor flows and an influent waste water stream flows prior to introduction to the reactor.
The improvement comprises a first double pipe heat exchanger for an influent stream and a second double pipe heat exchanger for an effluent stream. The first and second heat exchangers each have a tube side inlet and an annular space inlet. A first conduit delivers an influent stream to the tube side inlet of the first heat exchanger. A second conduit delivers an effluent stream from the reactor to the tube side inlet of the second heat exchanger. The first and second heat exchangers have a tube side outlet and an annular space outlet. Means is provided for circulating a heat exchange medium through the annular space inlets and outlets of the first and second heat exchangers to preheat an influent stream prior to introduction to the reactor where energy for preheating is extracted from an effluent stream passing through the second heat exchanger, whereby influent and effluent streams pass through the tube side of each of the first and second heat exchangers to minimize clogging of the first and second heat exchangers.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention will be discussed with respect to the reactor system schematically shown in FIG. 1 of the drawings; and
FIG. 2 is a section through a representative type of double pipe heat exchanger taken along the lines 2--2 of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The operating temperature of the reactor system is normally in the range of 250° C. at an operating pressure of approximately 45 atmospheres. It is appreciated by those skilled in the art that variations in the temperature and pressures may be employed depending upon the condition of the waste waters to be treated. Hence the reactor 10, as shown in FIG. 1, is a closed system with an inlet 12 and an outlet 14. A level control generally designated 16 is provided within the reactor having a level probe portion 18, or other suitable level detection device, such as a differential pressure measuring device, ultrasonic level sensor or gamma radiation detection device. For example, the alternative pressure sensor could be calibrated to cause opening of the valve 24 when the pressure reaches 650 psi and to close the valve when the pressure drops to 600 psi. The purpose of the probe 18 is to sense the level of the reaction medium 20 within the reactor. The inlet 20 provides on a continuous basis a flow of waste waters to be treated. Once the probe 18 senses the medium level, a signal is generated in the level control device 16 and transmitted via line 22 to the outlet valve 24 having electronic controller 26. Upon receiving a signal in line 22 to open, the valve 24 remains open under the control of controller 26 for a predetermined period of time to lower the medium level 20 in the reactor 10 well below the probe 18. For example, when the system is adapted to treat approximately 1,000 gallons per day and in view of the high pressures within the reactor, an opening of the valve to a fully open position for approximately 2 to 5 seconds per minute is sufficient to drop the level of the medium in the reactor 10. With the continuous inlet flow, the medium level continues to rise in the reactor until the probe 18 senses the medium again to actuate the cycle all over again to partly drain the reactor. Hence there is a continuous inflow of waste waters to be treated and an intermittent outflow of effluent at the outlet 14.
To capture the heat in the outlet stream in line 28, a heat exchanger 30 is provided through which the effluent passes. The inlet to the heat exchanger is at 32. The outlet for the effluent is at 34. The heat exchanger 30 is in the form of a tube-in-tube heat exchanger, as shown in more detail in FIG. 2. The heat exchanger 30 has an outer tubular shell 36 with an inner tube 38 passing therethrough. The end 40 of the heat exchanger is sealed at 42 about the perimeter of the tube 38. Hence the effluent inlet is defined at 32. The effluent travels in the direction of arrow 44 through the interior 46 of the tube 38.
As shown in FIG. 1, a heat exchange medium is introduced at 48 to the heat exchanger 30 with an outlet at 50. In accordance with this embodiment, as shown in FIG. 2, the cooling medium travels in the direction of arrows 52 to the outlet 50. The heat exchange medium then flows in a counterflow direction relative to the direction of flow of the effluent through the tube into the heat exchanger. In this manner, the effluent travels straight through the heat exchanger 30 without encountering any obstructions. Hence as the effluent cools down under exchange with the heat exchange medium 52, solids do not build up on any obstructions within the heat exchanger. The valve 24, when fully opened, causes sufficient turbulence within the heat exchanger to clear out any solids which may deposit within the short time during which the reactor is being replenished with incoming waste waters to be treated.
The incoming waste waters are provided in line 54 to the inlet of pump 56. The pump 56 produces sufficient pressure in line 58 which is slightly in excess of the pressure in the reactor 10 to feed the waste waters to the inlet heat exchanger 60. The inlet to the heat exchanger is at 62 with an outlet at 64. The construction of the tube-in-tube heat exchanger 60 is the same as that of heat exchanger 30. The heat exchange medium is introduced to heat exchanger 60 at the inlet 66 and flows countercurrent to the flow of the waste waters and is removed from the heat exchanger at 68. The waste waters as heated in heat exchanger 60 pass along line 70 to the inlet 12 of the reactor 10.
The heat exchange medium is circulated through the outlet heat exchanger 30 and the inlet heat exchanger 60 via the pump 72. The heat exchange medium is introduced to the surge tank 74 which has an outlet 76 connected to the inlet of the pump 72. The outlet of the pump 72 feeds into line 78 which is in turn connected to the inlet 48 of the heat exchanger 30. The heat exchange medium may then be continuously circulated between the two heat exchangers 30 and 60. The purpose of the surge tanks 74 is to ensure that heat exchange medium is always present at the pump suction or inlet side of the pump 72.
According to a preferred embodiment of this invention, a temperature sensor 71 is provided in line 70. The temperature sensor 71 has an input to pump controller 73 via line 75. The controller 73 inputs and controls the speed of the pump 72 via line 77. The controller has a suitable input device, such as a keyboard, to permit entry of the desired temperature in line 70. The controller 73 then varies the speed of the pump 72 to adjust the flow rate of the heat exchange medium in the correct direction until the desired temperature in line 70 is achieved. It is appreciated, however, that the heat exchanger could be sized to produce the desired temperature profile and hence temperature in line 70.
In this manner the incoming waste waters are heated in a heat exchanger separate from the heat exchanger which cools down the effluent. This greatly simplifies the overall operation of the system allowing the independent operation of the reactor 10, while at the same time extracting heat from the effluent and not clogging of the system in either the reactor or the influent or effluent heat exchangers.
Since there may also be solids creation within the reactor 10, the inlet to the reactor is located above the medium level 80 so that solids cannot clog up the inlet 12. Further considerations in the operation of the system is with respect to the outlet valve 24. Preferably this is of a ball type valve construction with fully open and closed positions to avoid clogging and abrasion of the valve when open. It is also appreciated that, by the intermittent opening and closing of the valve 24, the flow of effluent is intermittent through the heat exchanger 30. However, with the continuous flow of the heat exchange medium through the outlet heat exchanger when there is a sudden flow of effluent, the substantial rise in temperature within the heat exchanger is immediately counter-reacted by the constant flow of the heat exchange medium to optimize on removal of heat from the effluent and in turn heating of the incoming waste waters to a mid-range of temperature prior to entry to the reactor. The moderation of temperature affected by the heat exchange medium also minimizes the potential for scale formation on the tube walls of the incoming waste waters.
Under use conditions, the temperature of the reactor 10 may be in the range of 225° C. to 275° C. with an operating pressure of approximately 500 to 1000 psi. The volume of the reactor is selected to provide for residence time of a few minutes up to approximately 5 hours, this, of course, being dependent upon the type of cyanide present in the waste waters and the operating temperature of the reactor. The effluent will usually emerge from the outlet heat exchanger at a temperature in the range of 70° C. in outlet 34. The heat exchange medium, as it emerges from line 50 of the heat exchanger, will normally be at a temperature in the range of 230° C.. The heating medium, as it exits the inlet heat exchanger in line 68, will be at a temperature in the range of approximately 38° C.. As a result, the heat exchange medium as it enters the heat exchanger 30 in line 48 will be at roughly the same temperature of 38° C.. The incoming waste waters, as they exit the heat exchanger 60, will be at a temperature in the range of 190° C..
It has been discovered that, by controlling the temperature of the waste water effluent from the first heat exchanger, significant advantages can be realized with this double heat exchange system. The temperature of the waste waters in the first heat exchanger is increased only to an upper maximum which avoids any significant hydrolysis of the cyanides. The reason for this is that premature hydrolysis of the cyanides in the heat exchanger can cause a scale formation on the exchanger interior. By use of the heat exchange system of this invention, the temperature of the waste waters can be controlled without causing any reaction of the cyanides by varying the rate of circulation of the heat exchange medium circulating between the inlet and outlet heat exchangers. If the pump speed is increased, the the waste waters are heated to a lower temperature whereas if the pump speed is reduced, then the waste waters are heated to a higher temperature. Hence control of the pump speed can adjust the temperature of the waste waters to a level just below the maximum temperature which would induce significant reactions of the cyanide.
Without the heat exchange system of this invention, such control on the waste water temperature cannot be achieved. If the incoming waste waters are heat exchanged directly with the reactor effluent, a large temperature gradient across the waste water stream develops because of the very high temperature of the reactor effluent. The large temperature gradient results in significant hydrolysis of the cyanides and formation of a scale on the hot surfaces of the heat exchange. Such baked on scale is very difficult to remove. This large temperature gradient in the incoming waste or reactor effluent is avoided in the heat exchange system of this invention so that baked on scale build-up in the heat exchangers is avoided.
The apparatus in providing for an integrated network of two heat exchangers transferring heat from the effluent to the incoming waste waters minimizes clogging of the system. Waste waters only flow through the tube side and not through the annular spaces. Hence the probability of plugging either heat exchanger is reduced as no sharp corners are present and flow tolerances are greater on the tube side. If in some event blockages or obstructions do occur in either heat exchanger, they are very easily cleared from the tube side of the heat exchanger. Temperature gradients are reduced significantly within the heat exchangers which lowers the possibility of scaling on the walls, particularly in the first heat exchanger. The reactor is designed to provide for intermittent discharge of effluent for brief intervals in a manner which also avoids solids build-up in the system. This avoids the need for some other form of continuous discharge effluent which is normally the case with a continuous provision of incoming waste waters. As a result, no proportional control valves are needed which would readily clog and suffer severe abrasion.
Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.
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A waste water treatment system for high temperature hydrolysis of cyanides has a reactor operating at a sufficiently high temperature and pressure to effect hydrolysis of cyanide in the waste waters. A heat exchanger system is provided through which reactor effluent and reactor influent streams flow. The improved waste water treatment system includes a first tube in tube heat exchanger for an influent stream and a second tube in tube heat exchanger for an effluent stream. A heat exchange medium is circulated between the effluent heat exchanger and the influent heat exchanger to cool down the effluent and in turn use the heat to heat up the influent to the reactor. The heat exchangers are arranged such that the influent and effluent streams pass through the tube side of each heat exchanger to minimize clogging of the first and second heat exchangers, while at the same time providing for effective heat exchange in cooling the effluent and heating up the waste waters to be treated.
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CROSS-REFERENCE TO RELATED APPLICATIONS
The following is based on and claims priority to Provisional Application Ser. No. 60/408,279, filed Sep. 5, 2002 and to Provisional Application Ser. No. 60/385,272, filed Jun. 3, 2002.
BACKGROUND
In a variety of subterranean environments, such as wellbore environments, tubing is deployed in sections that are sequentially connected. For example, sections of production tubing may be threaded together as tubing is continually run into a wellbore. Additionally, tubular members, such as sand screens and other wellbore completion components, are connected as such systems are moved downhole. Some existing tubular members comprise a joint area with a fixed shoulder that rests on plates of a screen table while the next sequential member is connected. However, new component designs, e.g. new sand screen designs, may be made without shoulders and without threaded engagement features. Accordingly, existing handling and assembly equipment may not be adequate for handling such components.
SUMMARY
In general, the present invention provides handling and assembly equipment. Embodiments of the handling and assembly equipment provide for downhole applications using a variety of sand screen as well as other wellbore component configurations.
BRIEF DESCRIPTION OF THE DRAWINGS
Certain exemplary embodiments of the invention will hereafter be described with reference to the accompanying drawings, wherein like referenced numerals denote elements, and;
FIG. 1 is a schematic illustration of a handling and assembling system, according to an embodiment of the present invention;
FIG. 2 is an isometric view of an assembly press according to one embodiment of the invention;
FIG. 3 is an isometric view of an embodiment of an upper or lower clamp illustrated in FIG. 1 ;
FIG. 4 is an isometric view of a lifting wrap according to an embodiment of the present invention;
FIG. 5 is an isometric view of an embodiment of a wrap key used with the lifting wrap illustrated in FIG. 4 ;
FIG. 6 is generally an axial cross-sectional view illustrating the lifting wrap of FIG. 4 combined with a sand screen;
FIG. 7 is a cross-sectional view of an embodiment of an upper sub assembly taken generally along its axis;
FIG. 8 is a cross-sectional view similar to FIG. 7 ;
FIG. 9 is another cross sectional view similar to FIG. 7 ;
FIG. 10 is a front view of an embodiment of a screen having a hanging wrap profile;
FIG. 11 is an isometric view of an embodiment of a shoulder key for use with a shoulder wrap;
FIG. 12 is an isometric view of another embodiment of a shoulder wrap;
FIG. 13A is a front view of the shoulder wrap and screen illustrated in FIG. 12 disposed on screen table plates;
FIG. 13B is a front view similar to FIG. 13A but showing an alternate shoulder wrap;
FIG. 14 is a front view of a tubular member having an embodiment of a slip gripping area; and
FIG. 15 is a front view of the tubular member illustrated in FIG. 14 with slips applied to the slip gripping area.
DETAILED DESCRIPTION
In the following description, numerous details are set forth to provide an understanding of the present invention. However, it will be understood by those of ordinary skill in the art that the present invention may be practiced without these details and that numerous variations or modifications from the described embodiments may be possible.
The present invention generally relates to handling and assembly equipment and related methods. These equipment and methods are useful with, for example, tubulars fitted with bayonet-type connectors. However, the equipment and methods of the present invention are not limited to use with those specific type connectors and corresponding tubulars. The present invention may be used with other tubulars and other types of equipment. For example, the present invention may be useful with sand screens, well equipment having stab-in type connections, expandable tubing, expandable sand screens and other well equipment components and connections.
Referring generally to FIG. 1 , a system 20 is illustrated according to an embodiment of the present invention. The system 20 comprises an assembly tool 22 to facilitate the sequential assembly of tubular components that are deployed in, for example, a wellbore 24 . For example, a tubular component 26 , such as a sand screen, may be held by assembly tool 22 while another tubular member 28 , e.g. production tubing or sand screen section, is connected to sand screen 26 . Tubular members 26 and 28 are described to aid in the description of system 20 , however a variety of other types of downhole components can be utilized in the system.
The upper tubular member 28 is brought into proximity with lower tubular member 26 to enable coupling of the tubular members via assembly tool 22 . Tubular member 28 may be moved towards assembly tool 22 and tubular member 26 by a lifting elevator 30 , such as the type utilized with a rig. Lifting elevator 30 may be connected to tubular member 28 through a damper unit 32 that aids in the connection of tubing members as well as the loading and unloading of the tubing string as sequential tubular members are added to the string.
In FIG. 2 , an embodiment of assembly tool 22 is illustrated. In this embodiment, assembly tool 22 comprises an assembly press 34 having a frame 36 , a securing system 37 , such as a spider 38 , an upper clamp 40 , a lower clamp 42 and a linear actuator 44 , such as a moving platform. Frame 36 comprises a linear guide 46 along which platform 44 moves in a linear, e.g. vertical, direction. Spider 38 is used to hang the tubular members, e.g. sand screen 26 , at the rig floor surface during assembly of subsequent tubular members.
Although spider 38 is illustrated for hanging the string at the rig floor surface during assembly of tubular components, other devices, such as screen table plates, can be utilized as described in greater detail below. Examples of spiders that can be used in assembly tool 22 are commercially available spiders, such as the CAVINS ‘Advance’ spider available from Cavins Oil Well Tools of Long Beach, Calif., U.S.A. and illustrated at the Cavins website http://www.cavins.com/. The spider has hydraulically activated slips for holding tubular members at the rig floor. Such spiders come in a variety of sizes for various diameter pipes and other tubular members. It also should be noted that the handling of tubular members by spider 38 can be enhanced with the use of slip liners designed for “non-marking” applications, such as slip liners available from Cheyenne Services, Inc. of Houston, Tex. The slip liners provide smooth slip inserts able to hold the tubing string in the spider slips without substantial marking of the tubular members.
During assembly of a tubular string, assembly tool 22 is used to hold the string, e.g. an expandable screen string, at the surface while assembling or disassembling connections. For assembly, the first tubular member 26 is lowered into the spider 38 and the slips are closed to hang the tubular member 26 , e.g. a sand screen section. The next tubular member 28 is then lowered into place over member 26 , as illustrated in FIG. 1 , such that the ends of the tubular members are aligned. The moving platform 44 with upper clamp 40 is then moved towards tubular member 28 until upper clamp 40 may be closed on tubular member 28 . Platform 44 is then moved downwardly until a lower end 45 of tubular member 28 is snapped or otherwise joined to an upper end 47 of tubular member 26 (see FIG. 1 ). Following completion of the assembly, the upper clamp 40 is opened followed by release of spider 38 such that the tubing string may be run-in-hole until positioned for the next joint assembly. This process is continued until the screen string or other tubular string is completely assembled.
For disassembly, the connection to be disconnected is moved into position below upper clamp 40 and securing system 37 , e.g. spider 38 , is set. Then, upper clamp 40 is clamped to the upper tubular member while lower clamp 42 is clamped to the lower tubular member. Actuating platform 44 moves upper clamp 40 upwardly along linear guide 46 to linearly disconnect the tubular members. The remaining tubing string is once again lifted to enable disconnection of the next joint, and this process is continued until the desired state of disassembly is achieved.
In the embodiment illustrated, moving platform 44 is hydraulically actuated. However, platform 44 may be moved by a variety of other actuators, such as pneumatic actuators, ball screws and other mechanisms.
An embodiment of upper and lower clamps 40 , 42 is illustrated in FIG. 3 . In this embodiment, each clamp 40 , 42 utilizes at least one hydraulic cylinder 48 , e.g. two hydraulic cylinders 48 , coupled to at least two C-shaped clamp faces 50 via linkage mechanisms 52 . Linkage mechanisms 52 are slideably or pivotably mounted within a clamp framework 54 to move C-shaped clamp faces towards and away from each other upon actuation via hydraulic cylinder 48 . The C-shaped clamps are designed to hold with enough force for the assembly and/or disassembly of the tubing string joints. The linear guide 46 maintains the upper clamp 40 and lower clamp 42 in general alignment.
Referring generally to FIGS. 4–6 , a lifting mechanism 56 for moving tubular members, such as a tubular sand screen, is illustrated. Lifting mechanism 56 is designed to selectively couple a tubular member, e.g. tubular member 26 or 28 , to an appropriate deployment system, such as a lifting elevator 30 or the combined lifting elevator 30 and damper unit 32 . In the embodiment illustrated in FIGS. 4–6 , lifting mechanism 56 comprises a mandrel 58 and a lifting wrap 60 for selectively coupling mandrel 58 to a tubular member, such as tubular member 26 . In this embodiment, mandrel 58 may be connected to damper unit 32 either directly or by an appropriate connector or coupling. The mandrel 58 and lifting wrap 60 may be used to securely grab the end of a tubular member to lift the member in and out of wellbore 24 . As illustrated in FIGS. 4 and 5 , an embodiment of lifting mechanism 56 comprises a plurality of lifting keys 62 . Each lifting key 62 comprises at least a pair of pivot features 64 that may have tabs 66 with openings 68 for receiving pivot pins 70 . Thus, each lifting key 62 may be pivoted with respect to the adjacent lifting keys to which it is pivotably attached via pivot pins 70 . Lifting wrap 60 is wrapped around a tubular member and connected by a final connector pin 72 , as illustrated in FIG. 4 .
In the embodiment illustrated, each lifting key 62 also comprises an engagement feature 74 able to engage both mandrel 58 and a selected tubing component, such as sand screen 26 . As illustrated in FIG. 5 , engagement feature 74 may comprise a pair of extensions 76 configured to engage corresponding features 78 of mandrel 58 and tubular member 26 . In this embodiment, corresponding features 78 comprise a mandrel shoulder 80 extending radially upward from mandrel 58 and an opening or recess 82 formed in the sidewall of tubular member 26 .
To connect lifting mechanism 56 to tubular member 26 , a lead end 84 of mandrel 58 is inserted into the interior of tubular member 26 until the upper extent of tubular member 26 is adjacent a lower end of mandrel shoulder 80 . The lifting wrap 60 is then wrapped around mandrel 58 and tubing member 26 , such that the lower extensions 76 of each lifting key 62 engage corresponding openings 82 formed in tubular member 26 . Simultaneously, each upper extension 76 of lifting key 62 is engaged with mandrel 58 above shoulder 80 to affectively secure mandrel 58 to the upper end of tubular member 26 . Upon insertion of the final connector pin 72 , the tubular member 26 may be lifted and moved via mandrel 58 . For example, tubular member 26 may be moved into position for connection to the next adjacent tubular member. Mandrel 58 may be released from tubular member 26 by releasing and unwrapping lifting wrap 60 . Similarly, mandrel 58 and lifting wrap 60 may be coupled to a tubular that is to be disconnected and lifted away from an adjacent tubular.
Mandrel 58 may be connected to or formed as part of damper unit 32 which serves as an upper subassembly to accommodate movement of the tubular members during assembly. As illustrated in FIGS. 7–9 , an embodiment of damper unit 32 enables the movement of the upper screen 28 towards lower screen 26 . The damper unit contains a mechanism to absorb the movement of the upper tubular member during assembly and to dampen movement upon release from the tubing string.
As illustrated in FIG. 7 , damper unit 32 comprises an external housing 86 coupled to a pair of end caps 88 , 90 . A shaft 92 is slideably mounted through end cap 88 and comprises a connector end 94 appropriately designed for connection with lifting elevator 30 . Opposite connector end 94 , shaft 92 is coupled to a piston 96 . Piston 96 has a generally hollow interior 98 and a distal flange 100 . A spring 102 , such as a coil spring, is disposed within external housing 86 between end cap 88 and distal flange 100 to bias piston 96 towards end cap 90 .
Within hollow interior 98 , a damper piston 104 is slideably positioned and coupled to end cap 90 by, for example, a shaft 106 . Damper piston 104 comprises a flow control system 108 . Additionally, damper unit 32 comprises an extension 110 that is coupled to end cap 90 and extends from end cap 90 to a connector end 112 designed to engage and lift the appropriate tubular members. For example, connector end 112 may be designed to latch to mandrel 58 .
Referring specifically to FIGS. 8 and 9 , operation of damper unit 32 can be further described. It should be noted that in FIGS. 8 and 9 , the damper unit has been illustrated without spring 102 . In FIG. 8 , damper unit 32 is shown in an unloaded state. As the string load is applied to damper unit 32 at connector end 112 , spring 102 is compressed, and the compression continues with the downforce of the overall tooling increasing until piston 96 abuts against end cap 88 , as illustrated best in FIG. 9 . The additional string load is carried through the shouldering interface between end cap 88 and piston 96 . Furthermore, as piston 96 moves from the unloaded state, illustrated in FIG. 8 , to the loaded state, illustrated in FIG. 9 , damper piston 104 translates through the hollow interior 98 of piston 96 . During this translation, a hydraulic fluid 114 within hollow interior 98 passes through flow control system 108 of damper piston 104 to an opposite side of damper piston 104 , as illustrated in FIG. 9 . Flow control system 108 is designed to permit relatively easy oil flow through damper piston 104 during loading of the tool and substantially more restricted flow upon unloading of damper unit 32 . For example, flow control system 108 may be designed such that as loading occurs, hydraulic oil moves valve plates to expose large holes for easy flow between chambers, i.e. from the right side of damper piston 104 ( FIG. 8 ) to the left side of damper piston 104 ( FIG. 9 ). When damper unit 32 is unloaded, however, the oil pushes the valve plates closed to cover the large holes. Small orifice holes formed either through the valve plates or other parts of damper piston 104 restrict the flow as damper unit 32 transitions from the loaded to the unloaded state. Thus, the energy is allowed to dissipate slowly and in a controlled manner during release of the damper unit or failure of a system component.
System 20 is amenable to the relatively rapid assembly and disassembly of tubular members that have linear type connectors, such as connectors that stab into one another to form a connection. Although a wide variety of configurations, orientations, sizes and profiles can be used to form such linear connectors, an example is illustrated in FIG. 10 . In this design, the tubular member 26 comprises a linear connector end 116 , such as a stab-in connector. Linear connector end 116 is designed to linearly engage a similar, corresponding connector end disposed on the next adjacent tubular member, e.g. tubular member 28 , to form a tubing string joint as the tubing members are linearly engaged. In this embodiment, tubular member 26 does not have a permanent shoulder, but instead has a plurality of fingers 118 . Each finger 118 includes a stab-in connector head 120 designed to linearly engage corresponding connector heads 120 on the next sequential tubular member. Additionally, linear connector end 116 comprises openings 82 , as described above with reference to FIG. 6 . Openings 82 are sized to receive extensions 76 of lifting keys 62 when lifting wrap 60 is wrapped around tubular member 26 and mandrel 58 .
Alternatively, a different embodiment of lifting wrap 60 can be used in conjunction with linear connector ends 116 of tubular members, such as tubular members 26 and 28 . In this embodiment, a plurality of shoulder keys 122 (see FIG. 11 ) are pivotably connected as illustrated in FIG. 12 . For example, each shoulder key 122 may comprise a pair of opposed flanges 124 that are pivotably connected to one another via, for example, openings 126 and corresponding pivot pins. The plurality of pivotably connected shoulders keys 122 are combined to form a shoulder wrap 128 that securely engages the tubular member, e.g. sand screen 26 . In the example illustrated, each shoulder key 122 comprises an engagement feature 130 that enters a corresponding opening 131 when shoulder wrap 128 is wrapped around tubular member 26 and pinned together with a final retention pin, as described with respect to lifting wrap 60 .
In this embodiment, shoulder keys 122 are combined into shoulder wrap 128 which creates a removable shoulder that may be selectively attached to each tubular member. The removable shoulder can be utilized with, for example, a hanging plate 132 , e.g. a screen table plate, as illustrated in FIG. 13A . The shoulder wrap 128 is coupled to the tubular member, e.g. tubular member 26 , and hung from a hanging plate 132 . Thus, in some embodiments and applications, spider 38 may be replaced or supplemented by hanging plate 132 . Additionally, the shoulder wrap 128 can be used independently with hanging plate 132 or other hanging devices.
Another embodiment of a shoulder wrap 128 is illustrated in FIG. 13B . In this embodiment, shoulder wrap 128 is designed for engagement with a tubular member, e.g. tubular member 26 , via a profile 134 , such as a plurality of grooves and ridges, as illustrated by hidden lines in FIG. 13B . The profile 134 may comprise other features, such as notches, dimples and other types of profiles able to support increased axial loading. In the illustrated embodiment, profile 134 is directed inwardly for engagement with a corresponding profile 136 , e.g. grooves and ridges, formed in tubular 26 .
Although the profile 134 may be formed in a variety of components, one example utilizes a pair of generally C-shaped collar members 138 pivotably connected via a pivot 140 , such as a pivot pin. Thus, collar members 138 may be pivoted between an opened position and a closed position in engagement with corresponding profile 136 . A fastener 142 , such as a threaded fastener, can be connected between collar members 138 to securely force collar members 138 to a closed position over corresponding grooves and ridges 136 . Thus, the weight of tubular member 26 along with any appropriate suspended tubing string can be supported by shoulder wrap 128 on, for example, hanging plate 132 . Furthermore, during assembly or disassembly of the tubular members, the shoulder wrap 128 may be selectively disengaged and reengaged with subsequent tubular members.
The shoulder wrap illustrated in FIG. 13B also may comprise an abutment 141 , such as a pin, that extends into a corresponding feature of the tubular member or a coupling connected to the tubular member. Abutment 141 prevents relative rotation between collar members 138 and the tubular member. Furthermore, the shoulder wrap may comprise an interfering profile 143 positioned to engage a corresponding feature on hanging plate 132 . Profile 143 prevents rotation of the shoulder wrap relative to hanging plate 132 during assembly or disassembly of tubular components. The abutment 141 and profile 143 enable the coupling of a wide variety of tubulars including tubulars that are threaded together. For example, connector end 116 may be replaced with a threaded connector. In one embodiment, a lifting sub connected to lifting elevator 30 is coupled to a tubular via the shoulder wrap and a coupling. The lifting sub and the coupling are connected by a lift sub ring that attaches to the coupling with left handed threads. The left handed threads prevent unthreading/disconnection of the lift sub during connection of tubulars having threaded connector ends.
In an alternate embodiment, openings 131 are replaced with another type of engagement feature, as illustrated in FIGS. 14 and 15 . In this embodiment, a tubular member, such as sand screen 26 , comprises a plurality of thin slots that can be arranged in a variety of cell patterns along the tubular member. The thin slots 144 are transitioned to expanded slot regions 146 that form a slip grip area 148 . The increased slot width allows the screen 26 to be compressed when squeezed by, for example, a plurality of slips 150 , as illustrated in FIG. 15 . Slips 150 may be of the type used with spider 38 . When slip grip area 148 is squeezed by slips 150 , the sand screen is radially compressed to a smaller diameter relative to the unsqueezed tubular portions. The smaller diameter creates a shoulder 152 that rests on an upper edge of slips 150 and provides mechanical holding power. Thus, this type of engagement feature allows each tubular member to be held by assembly tool 22 during coupling with the next sequential tubular member moved linearly into engagement with the hanging member.
Although only a few embodiments of the present invention have been described in detail above, those of ordinary skill in the art or readily appreciate that many modifications are possible without materially departing from the teachings of this invention. Accordingly, such modifications are intended to be included within the scope of this invention as defined in the claims.
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A handling and assembly system and method for use in deploying tubing in a subterranean environment. A framework is used to linearly engage sequential tubular members as a tubing string is formed and run into a subterranean environment. The system also facilitates the disassembly of the individual tubular components from the tubing string.
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FIELD OF THE INVENTION
The present invention relates to fabric bleaching processes generally, and particularly relates to an improved bleaching process for denim goods which reduces the number of undesirable bleach streaks on the goods being treated and which can provide other special surface styling effects.
BACKGROUND OF THE INVENTION
Denim garments such as slacks, jackets and skirts are considered by many to be more fashionable once they have attained a faded, worn appearance. Accordingly, denim fabrics and garments are frequently subjected to a bleaching procedure during their manufacture to give them a bleached, superbleached, rifled or whitewashed appearance. While such prebleached goods are a very marketable product, the bleaching procedures conventionally employed are relatively labor intensive, which adds significantly to the cost of the bleaching process. Also, the conventional bleaching procedures can produce undesirably high levels of second quality goods, due primarily to streaks in the goods.
Most streaks occur along the fold lines of garments and fabrics which have been stiffened with starch sizing. At these folds, the stiffness of the sized fabric apparently spreads out the individual fibers of the fabric, subjecting these fibers to greater bleaching action. When a high quality, uniform prebleached appearance is desired, some special procedure must be employed to minimize streaking. A typical procedure is as follows: (a) garments are turned inside out to break fold lines; (b) the garments are placed in a laundry machine and desized; (c) the garments are removed from the machine and turned right-side out; (d) the garments are placed back in the laundry machine and bleached. The need for turning the garment inside out and then right-side out obviously both slows this process and adds significant labor costs. Moreover, a significant number of bleached garments will be unacceptable, even under this careful and elaborate procedure, when quality control standards are high and few streaks are tolerated. Where less rigorous quality control standards are imposed--as may be the case when some streaking is considered stylish--garments need not be turned and returned prior to bleaching. Even with this simplified procedure, it is still, nevertheless, generally necessary to desize the garment prior to bleaching, to prevent very pronounced streaks from appearing.
Accordingly, a primary object of the present invention is to provide a bleaching process which imparts a uniform prebleached appearance to garments, especially denim garments. An additional object is to provide a bleaching process which provides aesthetically pleasing surface bleaching styling effects. Still another object is to provide a bleaching process which eliminates the need for turning and returning garments so that the efficiency of the bleaching process is increased. A still further object is to provide a bleaching process for denim goods which, if desired, will produce goods having an acceptable faded appearance without even the need for desizing the goods prior to bleaching.
DESCRIPTION OF THE INVENTION
The foregoing and other objects and advantages are achieved by using a polyacrylic acid (PAA) in a bleach bath during the processing of the goods. Specifically, the present invention involves the use of PAA in what is known in the industry as a "long bath" i.e. a bath in which the ratio, by weight, of the bath itself to the goods placed in the bath is greater than 3:1, and typically ranges from about 8:1 to about 40:1.
The method of the present invention comprises the steps of immersing the fabric or garment to be bleached in an aqueous bleach bath containing a bleaching agent and a polyacrylic acid, and maintaining the fabric in the bleach bath for a time sufficient to bleach the fabric. The polyacrylic acid, discussed in greater detail below, is preferably included in a concentration of from about 0.01 to about 10 grams per liter. The bleach bath solution has a watery consistency with a noticably slippery feel which lubricates the fibers of the fabric during the bleaching cycle. An advantageous property of the polyacrylic acid is that it builds viscosity, even at relatively low concentrations. Also, it has a very low solids content so that it can be easily removed from the fabric by rinsing. Moreover, certain chemicals function as viscosity reducing agents and will destroy the viscosity building properties of the polyacrylic acid. To facilitate further processing of the garments or fabrics after bleaching, bleaching may be followed by the step of adding a viscosity-reducing agent to the bleach bath to thereby reduce the viscosity increasing effect of the PA and facilitate subsequent rinsing. Suitable viscosity-reducing agents include common salt or bisulfite, with bisulfite advantageously functioning also as an antichlor.
Although applicant does not wish to be bound to any theory of how the present invention works, the viscosity altering characteristics of the polyarylic acid appear to contribute to a more even bleaching. Our observations suggest that the presence of polyacrylic acid in the bleach bath slows down the bleaching action so that bleaching occurs during the entire bleach cycle. Without the polyacrylic acid, the bleaching occurs very quickly, immediately upon addition of the bleaching agent, with more streaks as a result. Polyacrylic acids of the type used in practicing the present invention have previously been used in textile processing applications as print paste thickeners and for producing styling effects in the dyeing of carpets, but, insofar as applicant is aware, have not previously been used in the manner disclosed herein.
The present invention is well suited for bleaching garments, particularly denim garments. When used for bleaching denim garments, the garment is preferably immersed in the bleach bath with its finished side out, thereby eliminating the need for turning the garment during the bleaching process. This provides a significant savings of labor and cost, and greatly increases the speed (throughput) of the bleaching operation. A preferred process for bleaching denim garments comprises the steps of (a) desizing the garment while the garments are right-side out and thereafter without turning the garment, (b) immersing the garment in an aqueous solution containing from about 0.01 to about 10 grams per liter of a polyacrylic acid, and then (c) adding a bleaching agent to the aqueous solution to produce a bleach bath, and then (d) maintaining the garment in the bleach bath for a time sufficient to bleach the garment. The procedure is preferably carried out in a heated bath, with a temperature of about 140 degrees Fahrenheit being typical. Through the use of this procedure, as explained in greater detail below, processing efficiency has been increased by thirty seven percent over production rates obtained with procedures requiring turning and returning of garments. At the same time, the quality of the garment finish was increased to such an extent that the number of garments rejected for excessive streaking was reduced from about fourteen percent to about five percent. When less rigorous quality control standards are applied, further cost savings can be achieved by using the inventive process without first desizing the garments, or fabrics, treated.
A suitable polyacrylic acid for use in the present invention can be easily selected. The polyacrylic acid selected should be viscosity stable at the bleach concentrations encountered during the processing of garments or fabrics in the bleach bath. The stability of various polyacrylic acids to chlorine and other bleaching agents is either known or easily determined. Polyacrylic acids for use in a preferred embodiment of this invention, where a concentrated polyacrylic acid stock solution is pumped into a bath, are also easily selected. For such a stock solution, a PAA should be selected which gives a sufficient increase in bath viscosity with a small volume of stock solution, yet gives a stock solution which is pumpable on standard equipment. By understanding the relation of viscosity to concentration in aqueous solution for various polyacrylic acids, a polyacrylic acid can be selected which provides a highly concentrated stock solution which is not so viscous that it cannot be pumped into a bleach bath, yet when the stock solution is pumped into a bleach bath and diluted, the viscosity of the bleach bath is increased. Viscosity curves giving this viscosity to concentration ratio are either known, or easily generated. To further simplify the selection of a suitable PAA for use in any embodiment of this invention, initial tests should be conducted with fabric swatches in a laboratory beaker, before commercial runs are attempted.
Through the use of the foregoing procedures, applicant selected "CARBOPOL 870" as a most preferred polyacrylic acid for carrying out this invention. "CARBOPOL 870" is a product of B.F. Goodrich Company, Specialty Polymers & Chemical Division, 6100 Oak Tree Boulevard, Cleveland, Ohio, 44131. CARBOPOL is a registered trademark of the B.F. Goodrich Company. As numerous other polyacrylic acids can easily be used to practice the present invention, this information is provided as an example only, and is not to be construed as limiting the scope of this invention. For example, the information provided by U.S. Pat. No. 2,244,703 to Hubbuch, U.S. Pat. No. 3,887,509 to Bolstad et al., U.S. Pat. No. 4,331,572 to Tomasi et al., and U.S. Pat. No. 4,386,120 to Sato et al. is all helpful in selecting polyacrylic acids useful for practicing the present invention. The disclosures of these patents are, therefore, to be incorporated herein by reference.
The following examples are provided to further illustrate the present invention. These examples are for illustrative purposes only, and are not to be taken as limiting.
EXAMPLE 1
Preparation of Concentrated PAA Stock Solution
A concentrated, aqueous polyacrylic acid solution was prepared by mixing "CARBOPOL 870" with 50% sodium hydroxide solution, at a proportion of one to one by weight, into water in a high speed mixer, while the mixer was running, along with a nonionic wetting agent. The proportions of the mixture, on a weight basis, was 8 parts "CARBOPOL 870," 8 parts sodium hydroxide and 4 parts wetting agent mixed with water to give a 12,000 centipoise solution. Though highly viscous, the solution was still capable of being pumped with standard commercial laundry equipment.
EXAMPLE 2
Bleaching of Garments
An 18 pound batch of new, sized, blue denim slacks, made from unbleached 15.5 ounce blue denim fabric, was placed in an 85 pound capacity laundering machine, and the machine filled with water heated to 140 degrees Fahrenheit. Six ounces of a nonionic softener/lubricant and six ounces of an anionic wetting agent were added, and the machine was run for five minutes. Four ounces of an enzyme desizing agent was then added, and the machine was run for an additional ten minutes. The machine was then drained and refilled with fresh water at 140 degrees Fahrenheit.
Five pounds, six ounces of the concentrated polyacrylic acid stock solution prepared in Example 1 was then added to the machine, so that the final concentration of polyacrylic acid in the machine was three tenths of a gram per liter. The machine was then run for two minutes. Two pounds of a hypochlorite bleaching agent were then added, and the machine was run for an additional ten minutes. The machine was then drained, refilled with fresh water, run for two minutes, drained again and the slacks spray rinsed. The machine was again refilled with fresh water, five ounces of sodium bisulfite, an antichlorine agent added, the machine run for five minutes, drained, and the slacks extracted for three minutes.
After extraction, the slacks were removed from the machine and inspected for defects. They were found to have a uniform prewashed appearance, and to be remarkably free of streaks along fold lines, seams, and the like. Moreover, those streaks which were present were less pronounced than those streaks found in denim slacks bleached by a conventional process, without the inclusion of a polyacrylic acid.
EXAMPLES 3-6
Effects of Varying Weight of Garment Load
The procedure described in Example 2 above was repeated with (3) an eighteen pound load of size 30" waist, 30" inseam slacks, using five pounds, six ounces of PAA stock solution and two pounds, one ounce of bleach; (4) a thirty-three pound load of size eighteen medium slacks, using nine pounds, six ounces of PAA stock solution and three pounds, fifteen ounces of bleach; (5) a twenty pound load of size seven youth's slacks, using six pounds of PAA stock solution and two pounds, six ounces of bleach; and (6) a twenty-six pound load of size eighteen medium slacks, using seven pounds, thirteen ounces of PAA stock solution and three pounds, two ounces of bleach. The quantities of both additives used during other stages of the process were adjusted according to the weight of the load, in accordance with conventional practice. The slacks were constructed of the same sized denim fabric described in Example 2.
After the bleaching procedures were completed, the slacks were inspected. The slacks were found to be uniformly bleached and without streaks. Only one dry bleach spot was observed. Accordingly, a liquid bleach system is recommended to avoid bleach spots, and to avoid any buildup of undissolved bleach in machines and drains.
The invention has been discussed with a degree of specificity above. This discussion has been provided for illustrative purposes only, with the scope of the invention being defined by the following claims.
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A process for bleaching fabrics or garments which produces a uniformly colored product with relatively few, less pronounced streaks is disclosed. The process requires fewer steps and increases efficiency over previous processes, while at the same time decreases the number of excessively streaked products which do not satisfy quality control standards. A preferred embodiment of the process, suited to denim fabrics or garments, comprises the steps of desizing the fabric or garment, and thereafter, without turning garments, immersing the fabric or garment in an aqueous solution containing from about 0.01 to about 10 grams per liter of a polyacrylic acid, and then adding a bleaching agent to the aqueous solution to produce a bleach bath. The fabric or garment is maintained in the bleach bath for a time sufficient to bleach the fabric or garment.
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FIELD OF THE INVENTION
The present invention relates to a device for electrostatically charging a multilayer ribbon or paper web train.
DESCRIPTION OF THE PRIOR ART
It is generally known and described in EP 0 230 305 A2 that in rotogravure printing the incoming material webs or respectively paper web train or ribbons, are made to adhere to each other electrostatically, which adheres is called ribbon adherence. The stability of the material webs or paper web trains is increased by means of this electrostatic interlocking, so that the danger of a formation of corners of the printed products in the folding apparatus is reduced. Electrodes, which are arranged at both sides of the material webs and at a distance from the material webs are provided for applying the electrostatic charge.
In connection with this electrostatic charge, its low effectiveness on the paper web train or ribbon is disadvantageous, so that it became necessary to arrange additional devices, for example electrostatically charged guide devices, as disclosed in EP 0 230 305 A2 in order to reduce the effects of the so-called whip action, which leads to the formation of corners.
DE 31 17 419 C2 describes a method for the electrostatic charging of a multilayer paper web train ribbon. Here, the ribbon is charged by means of contactless acting electrodes after the webs have been brought together to form a ribbon downstream of a pair of compression rollers.
DE 27 54 179 C2 discloses a method for the electrostatic charging of a multilayer ribbon, wherein the edge areas of each layer are individually charged by means of rollers.
EP 0378350 A2 discloses a transport device for paper sheets in a plotter. This transport device has transport rollers for electrostatically charging a paper sheet and a plastic sheet.
U.S. Pat. No. 4,462,528 A describes a device for holding a web. This device has brushes, by means of which the web is held electrostatically.
SUMMARY OF THE INVENTION
The present object of the invention is based on providing a device for the electrostatic charging of a multilayer ribbon.
In accordance with the invention, this object is attained by the use of two rollers which press the ribbon or paper web train together and which also act as charging electrodes. Alternatively, the paper web train or ribbon can be electrostatically charged by oppositely polarized charge electrodes in the form of electrically conductive brushes which touch the paper web train or ribbon.
The advantages which can be achieved by means of the invention lie, in particular, in that charging of the paper web train ribbon takes place in a manner which is so lasting, that further devices for preventing, or reducing the formation of corners can be omitted. For example, an already provided pair of drawing rollers, which is required for the operation of the folding apparatus and has been modified in its design for the purpose of transmitting a voltage, is used as the device for charging the ribbon.
The strength of the voltage required for charging the ribbon is reduced in comparison with the voltage required by the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of present the invention are represented in the drawings and will be described in greater detail in what follows.
Shown are in:
FIG. 1, a schematic representation of a longitudinal folding device, as well as the ribbon entry into a cylinder folding group;
FIG. 2, a longitudinal section through one roller of a pair of rollers of the present invention in accordance with FIG. 1;
FIG. 3, a representation analogous to FIG. 2, but with a second preferred embodiment; and in
FIG. 4, a representation analogous to FIG. 2, but with a third preferred embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A longitudinal folding device 3 with a pair of funnel folding rollers 4 , as well as two pairs of rollers, for example, drawing roller pairs 6 , 7 , are arranged ahead of the entry for a multilayer ribbon 1 , formed of for example, a plurality of paper webs, into a cylinder folding group 2 , for example, of a folding apparatus of a rotary printing press. This structure is depicted most clearly FIG. 1 .
The cylinder folding group 2 has a cutter cylinder 8 and a collection cylinder 9 , which operates against the cutter cylinder 8 and, in turn, works together with a folding jaw cylinder 11 . The printed products, which have been transversely folded in the cylinder folding group 2 , are supplied to a further processing station by means of a conveying device, for example a belt conveyor device which is not specifically shown in the drawings.
The second pair of drawing rollers 7 , arranged directly in front of the entry into the cylinder folding group 2 , consists of a first roller 13 , seated fixed in a lateral frame, and a second roller 16 , which is seated on a pivot arm or bearing element 14 as seen in FIG. 2 . This second roller 16 can be placed against the first roller 13 seated fixed in the lateral frame, with both rollers 13 and 16 of the second pair of drawing rollers 7 constituting the charging electrodes. The running paper web trainer ribbon 1 is conducted between the two rollers 13 , 16 .
In accordance with a first preferred embodiment as seen in FIG. 2 both rollers 13 , 16 consist of a cylinder- or hollow cylinder-shaped roller body, a metal body 17 , which has a shell 18 of a resilient covering of reduced conductivity, for example rubber of a hardness of approximately 85° Shore. The metal body 17 is connected, fixed against relative rotation, at both ends by means of hubs 19 —only one end being represented in FIG. 2 —with the shaft journal 21 .
The hubs 19 are fastened, electrically insulated, by means of ball bearings 22 in the bearing element 14 . An insulation which consists, for example, of respective bushings 23 of insulating material, for example a resin-bonded fabric, arranged between the pivot arm, or respectively the bearing element 14 , and the ball bearing 22 , which has a radial bore 24 for receiving a cable feed 26 . The cable feed 26 receives a feed line, for example a cable 27 which, for the purpose of transferring energy via an intermediate ring 25 , is pressed by means of a spring-loaded contact element 28 against the ball bearing 22 .
At its end remote from the roller 16 the shaft journal 21 is connected, fixed against relative rotation, with an annular flange 29 , which, in turn, is in connection, fixed against relative rotation, via a piece 31 of insulating material with a driveshaft 32 .
Each one of the rollers 13 , 16 of the second drawing roller pair 13 can be separately driven. Moreover, the first roller 13 of the second pair 7 of drawing rollers is connected with a negative pole of a d.c. source, not represented, of approximately 5 kilovolts, for example a high tension d.c. generator, and the second roller 16 of the second pair 7 of drawing rollers is connected with a positive pole of the d.c. source. The polarity can also be reversed.
The paper web train or ribbon 1 preferably consists of paper webs, which are weakly mineralized and highly resistive.
It is also possible to drive only one roller 13 or 16 of the pair of rollers 13 , 16 , or neither of the rollers of the pair of rollers 13 , 16 .
In accordance with a second preferred embodiment as seen in FIG. 3, both charge electrodes, which are designed as rollers 33 , 34 , also consist of a cylinder- or hollow cylinder-shaped metal body 36 , which has a multi-layer shell 37 comprised of with a lower, electrically insulating layer 38 , a center layer 39 which conducts electricity well, and an outer layer 40 , which is of only limited electrical conductivity.
At an end of each of the respective rollers 33 , 34 a metallic contact ring 42 is arranged on a roller end face. An interior diameter of contacting 42 is in connection with the shaft journal 43 , and a peripheral surface of contact ring 42 is in an electrically conducting connection with the electrically conducting center layer 39 of the roller shell 37 . This can be achieved, for example, in that the contact ring 42 has a shell-like contact surface 44 on its periphery, which extends concentrically in respect to the metal body 36 and which in turn supports contact tips 46 , which are arranged on the end face of contacting 42 in a ring shape, are spaced apart from each other and are connected with the material of the center layer 39 of shell 37 which center layer 39 conducts electricity well.
The shaft journals 43 —only one of which is represented—are seated in the bearing element 14 in bearings 47 , which are also surrounded by an insulating material 48 .
A wiper element 49 , which is fixed on the bearing element 14 and which is insulated against it, is connected with the contact surface 44 of the contacting 42 , and is pressed by means of a spring force against the contact surface 44 . As in the first preferred embodiment, the wiper element 49 is connected with a cable feed 26 4 and a cable 27 .
In accordance with a third preferred embodiment, as seen in FIG. 4, the rollers 51 , 52 which act as charge electrodes, respectively each consist of a stationary shaft journal 53 , fixed on the frame 14 in an insulating material 48 and having a roller body or metal body 36 . The metal body 36 is provided with an electrical high conductivity layer 39 , for example a steel shell, above which an outer layer 40 of limited electrical conductivity is arranged. One bearing 47 is arranged on both sides or ends of each of the rollers 51 , 52 between the shaft journal 53 and the steel shell 39 .
The supply of electrical energy to the rollers 51 , 52 takes By place via a cable 27 , which is in electrically conducting contact with the shaft journal 53 , for example with an exterior surface 54 of the shaft journal 53 .
It would, of course, also be possible to arrange the shell 39 , 40 fixedly on the metal body 36 and to seat the journals 53 , electrically insulated and rotatably in the bearing element 14 fixed in place in the lateral frame. In this case the cable 27 would have to be connected by means of a collector ring with the exterior 54 of the shaft journal 53 .
In accordance with a fourth preferred embodiment which is, not specifically represented, the transfer of electrical energy to the ribbon 1 can also take place by means of conducting brushes, for example carbon brushes, arranged on both sides of the material webs of the ribbon 1 .
It is furthermore possible to design the first and second rollers 13 , 16 , 33 , 34 , 51 , 52 of the second drawing roller pair 7 also in the form of so-called sandwich rollers.
Such sandwich rollers consist, for example, of a rotatably seated shaft, which receives a number of disks, which are arranged, fixed against relative rotation, on the shaft in the radial direction. Here, a disk made of metal, for example steel, alternates with an adjoining disk, which consists of a metal body having an electrically well conducting layer 39 , and above it an outer layer 40 of limited electrical conductivity such as shown in FIGS. 3 and 4. Electrical energy is introduced via the shaft journal.
Such a sandwich roller can be placed against a ribbon 1 as an individual roller, or also in opposing pairs, for example as a pair of drawing rollers.
When used in pairs, both sandwich rollers should be arranged in such a way that a metal disk of the first roller is placed opposite a layered disk of the second roller, and vice versa. Each roller of the pair of rollers has a different polarity.
While preferred embodiments of a method and a for electrostatically charging a multilayer train or paper web ribbon in accordance with the present invention have been set forth fully and completely hereinabove, it will be apparent to one of skill in the art that a number of changes in, for example, the source of drive power for the rollers, the specific type of printing press and folding group used and the like could be made without departing from the true spirit and scope of the present invention which is accordingly to be limited only by the following claims.
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A multiple layer paper web is provided with an electrostatic charge for the purpose of adhering the multiple webs to each other. A pair of oppositely charged rollers contact the surface of the multiple layer printing aper web and impart the charge to the web. The pair of oppositely charged rollers are positioned directly before a cylinder folding group of a web-fed rotary printing press.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of co-pending U.S. patent application Ser. No. 14/572,232 filed on Dec. 16, 2014, which claims the benefit under 35 U.S.C. §119(a) to Korean Patent Application No. 10-2013-0169271 filed on Dec. 31, 2013, all of which are hereby expressly incorporated by reference into the present application.
BACKGROUND OF THE DISCLOSURE
Field of the Invention
[0002] The present disclosure relates to a flexible display device, and particularly, to a flexible display device capable of preventing disconnection or short-circuiting of wires that may occur at a bending area during a bending process for a minimized bezel width, in an organic light-emitting diode display manufactured using a flexible substrate, and a method for fabricating the same.
Discussion of the Related Art
[0003] Among flat panel display devices proposed to replace the conventional cathode ray tube, an organic light-emitting diode (OLED) display has a characteristic that a light-emitting diode provided at a display panel has high brightness and a low operation voltage. Such OLED display has advantages that a contrast ratio is large because it is a spontaneous light-emission type, and a very thin display can be implemented. The OLED display can easily implement moving images because a response time is several micro seconds (μs). Further, the OLED display has an unlimited viewing angle, and is stably operated even at a low temperature.
[0004] In the OLED display device, display devices are formed on a substrate such as glass. Recently, a flexible organic light-emitting diode (OLED) display device, which is capable of maintaining a display function even when rolled (or bent) like paper due to its flexible material such as plastic or metal foil rather than a non-flexible substrate, has been developed.
[0005] FIG. 1 is a planar view schematically illustrating a flexible organic light-emitting diode (OLED) display device in accordance with the conventional art, and FIG. 2A is an enlarged view of part ‘A’ in FIG. 1 .
[0006] Referring to FIGS. 1 and 2A , the conventional flexible OLED display device 1 is formed on a flexible substrate 10 including an active area (A/A) and a non-active area (N/A).
[0007] The active area (A/A) is a region where an image is substantially displayed. A plurality of pixels (P) are arranged in the active area (A/A), in the form of matrices. Each of the pixels (P) includes a switching transistor (ST 1 ), a driving transistor (DT), a sensing transistor (ST 2 ), a capacitor (C), and an organic light-emitting diode (OLED).
[0008] The switching transistor (ST 1 ) of the pixel (P) is connected to a gate line (GL) and a data line (DL) which are formed in the active area (A/A) so as to cross each other. The driving transistor (DT) is connected to a driving voltage line 14 b for supplying a driving voltage (VDD) to the pixel (P) in the active area (A/A). The sensing transistor (ST 2 ) is connected to a reference voltage line 14 a for supplying a reference voltage (Vref) to the pixel (P) in the active area (A/A).
[0009] The non-active area (N/A) is a region formed around the active area (A/A), and is covered by a bezel portion, etc. Driving circuitry for driving the pixels (P) in the active area (A/A) and wires may be formed in the non-active area (N/A).
[0010] The driving circuitry includes a data driving portion 20 , a gate driving portion 13 and a light-emitting controller (not shown). The data driving portion 20 is mounted at a lower end non-active area (N/A) in the form of a chip. The gate driving portion 13 and the light-emitting controller are formed at one or more sides of the non-active area (N/A), in the form of a gate in panel (GIP).
[0011] Wires include power lines 14 a - 14 c , and signal lines GSL, DSL. The power lines 14 a - 14 c includes a driving voltage line 14 a , a reference voltage line 14 b and a ground line 14 c . Also, the signal lines GSL, DSL include a gate signal line (GSL), a data signal line (DSL) and a light-emitting signal line (not shown).
[0012] The driving voltage line 14 a outputs a driving voltage (VDD) provided from the data driving portion 20 to the pixel (P) in the active area (A/A). The reference voltage line 14 b outputs a reference voltage (Vref) provided from the data driving portion 20 to the pixel (P) in the active area (A/A). The ground line 14 c outputs a ground voltage (GND) provided from the data driving portion 20 to the pixel (P) in the active area (A/A).
[0013] The driving voltage line 14 a , the reference voltage line 14 b and the ground line 14 c include a region vertically extending from the data driving portion in the lower end non-active area (N/A), and a region formed in parallel to the data driving portion 20 .
[0014] That is, the driving voltage line 14 a , the reference voltage line 14 b and the ground line 14 c are extending from the data driving portion 20 in a vertical direction, at a region adjacent to the data driving portion 20 in the lower end non-active area (N/A). The driving voltage line 14 a , the reference voltage line 14 b and the ground line 14 c are formed as bars, in parallel to the data driving portion 20 , at a region adjacent to the active area (A/A) in the lower end non-active area (N/A).
[0015] The gate signal line (GSL) outputs a gate signal provided from the data driving portion 20 to the gate driving portion 13 . The data signal line (DSL) outputs a data signal provided from the data driving portion 20 to the data line (DL) in the active area (A/A). The light-emitting signal line outputs a light-emitting signal provided from the data driving portion 20 to the light-emitting controller.
[0016] In accordance with one embodiment, these wires may be formed to cross each other at least once, in the lower end non-active area (N/A). Thus, the power lines 14 a - 14 c and the signal lines GSL, DSL are formed on different layers, in order to prevent short-circuiting when the wires cross each other.
[0017] In the conventional flexible OLED display device 1 , the lower end non-active area (N/A) is formed to have a larger width than the rest of the non-active area (N/A). A bending area (B/A) is formed in the lower end non-active area (N/A), and part of the lower end non-active area (N/A) is bent to a rear surface of the flexible OLED display device 1 . Under such configuration, the width of the lower end non-active area (N/A) can be reduced.
[0018] FIG. 2B is a cross-sectional view of the flexible OLED display device of FIG. 1 , which illustrates a bent state.
[0019] Referring to FIG. 2B , reference numeral 11 denotes an organic light-emitting diode (OLED) formed in an active area (A/A), and reference numeral 12 denotes an encapsulation layer for encapsulating an OLED.
[0020] Referring to FIG. 2B , in the conventional flexible OLED display device 1 , the lower end non-active area (N/A) is bent based on a bending area (B/A), so that part of the lower end non-active area (N/A) can be positioned on a rear surface of the flexible OLED display device 1 . A curvature radius (R) of the bending area (B/A) is about 0.3 mm.
[0021] As mentioned above with reference to FIG. 2A , in the lower end non-active area (N/A) of the conventional flexible OLED display device 1 , wires are formed to cross each other. Thus, the power lines 14 a - 14 c and the signal lines GSL, DSL are formed on different layers.
[0022] However, because the wires are formed to cross each other even in the bending area (B/A), the wires may be disconnected from each other due to bending stress in the bending area (B/A).
[0023] FIG. 3 is a cross-sectional view taken along line in FIG. 2B .
[0024] Referring to FIG. 3 , the signal lines GSL, DSL and the power lines 14 a - 14 c are formed on different layers to thus be insulated from each other.
[0025] For instance, a gate signal line (GSL) and a data signal line (DSL) are formed on a flexible substrate 10 with a distance therebetween. A first insulating layer 15 is formed on the gate signal line (GSL) and the data signal line (DSL).
[0026] A driving voltage line 14 a and a ground line 14 c are formed on the first insulating layer 15 with a predetermined gap therebetween. The driving voltage line 14 a and the ground line 14 c are formed to overlap the gate signal line (GSL) and the data signal line (DSL), respectively. A second insulating layer 16 is formed on the driving voltage line 14 a and the ground line 14 c.
[0027] When the bending area (B/A) is bent with more than a predetermined curvature radius, cracks/breaks may occur at wires due to bending stress as shown in FIG. 3 (indicated by “a” and “b”). This may cause the wires to be disconnected from each other, or the insulating layer may be damaged to cause short-circuiting of the wires.
[0028] Such disconnection or short-circuiting of the wires may cause a malfunction of the flexible OLED display device 1 .
SUMMARY OF THE DISCLOSURE
[0029] Therefore, an aspect of the detailed description is to provide a flexible display device capable of preventing disconnection or short-circuiting of wires, by forming wires in a bending area of a non-active area, on the same layer so as not to cross each other, and a method for fabricating the same.
[0030] To achieve these and other advantages and in accordance with the purpose of this specification, as embodied and broadly described herein, there is provided a flexible display device, including: a flexible substrate having an active area where pixels provided with organic light-emitting diodes have been formed, a non-active area formed around the active area, and a bending area formed at a lower part of the non-active area; a data driving portion mounted in the lower end non-active area; a plurality of power lines formed in the lower end non-active area, and configured to supply power signals provided from the data driving portion to the active area; and a plurality of signal lines formed in the lower end non-active area, and configured to supply driving signals provided from the data driving portion to the active area, wherein the plurality of power lines and the plurality of signal lines are formed in the bending area, on the same layer in parallel to each other.
[0031] To achieve these and other advantages and in accordance with the purpose of this specification, as embodied and broadly described herein, there is also provided a method for fabricating a flexible display device, the method including: preparing a substrate having an active area, a non-active area, and a bending area formed at a lower part of the non-active area; forming a thin film transistor and an organic light-emitting diode on the active area of the substrate; and forming a plurality of power lines and a plurality of signal lines connected to the active area, on the lower end non-active area of the substrate, wherein the plurality of power lines and the plurality of signal lines are formed in the bending area on the same layer in parallel to each other.
[0032] The present invention can have the following advantages.
[0033] In the bending area of the non-active area, wires are formed on the same layer in parallel to each other, so as not to overlap or cross each other. As a result, disconnection or short-circuit of the wires, which occurs when the bending area is bent, can be prevented. Thus a malfunction of the flexible display device can be prevented.
[0034] Further scope of applicability of the present application will become more apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the disclosure, are given by way of illustration only, since various changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from the detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments and together with the description serve to explain the principles of the disclosure.
[0036] In the drawings:
[0037] FIG. 1 is a planar view schematically illustrating a flexible organic light-emitting diode (OLED) display device in accordance with the related art;
[0038] FIG. 2A is an enlarged view of part ‘A’ in FIG. 1 ;
[0039] FIG. 2B is a cross-sectional view of the flexible OLED display device of FIG. 1 , which illustrates a bent state;
[0040] FIG. 3 is a cross-sectional view taken along line in FIG. 2B ;
[0041] FIG. 4 is a planar view of a flexible OLED display device according to a first embodiment of the present invention;
[0042] FIG. 5 is an equivalent circuit diagram for a single pixel in the flexible OLED display device of FIG. 4 ;
[0043] FIG. 6 is a cross-sectional view taken along line VIa≠VIa′ and VIb˜VIb′ in the flexible OLED device of FIG. 4 ;
[0044] FIGS. 7A to 7C are views illustrating processes of fabricating a flexible OLED display device according to the first embodiment of the present invention;
[0045] FIG. 8 is a planar view of a flexible OLED display device according to a second embodiment of the present invention;
[0046] FIG. 9 is a cross-sectional view taken along line VII˜VII′ in the flexible OLED display device of FIG. 8 ;
[0047] FIG. 10 is a view illustrating a wire structure in a bending area in a flexible OLED display device according to the present invention; and
[0048] FIG. 11 is a view illustrating various embodiments of FIG. 10 .
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0049] Description will now be given in detail of the exemplary embodiments of the present invention, with reference to the accompanying drawings. For the sake of brief description with reference to the drawings, the same or equivalent components will be provided with the same reference numbers, and description thereof will not be repeated.
[0050] Hereinafter, a flexible display device and a method for fabricating the same according to the present invention will be explained in more detail.
[0051] FIG. 4 is a planar view of a flexible organic light-emitting diode (OLED) display device according to a first embodiment of the present invention.
[0052] Referring to FIG. 4 , the flexible OLED display device 100 according to a first embodiment of the present invention may be formed on a flexible substrate 110 including an active area (display area) (A/A) and a non-active area (non-display area) (N/A).
[0053] The active area (A/A) is a region where an image is substantially displayed. On the active area (A/A), a plurality of gate lines (GL) and a plurality of data lines (DL) may be formed to cross each other, thereby defining pixel regions. A plurality of sensing lines (SL) may be formed in parallel to the plurality of gate lines (GL).
[0054] Power lines for supplying a driving voltage (VDD), a reference voltage (Vref) and a ground voltage (GND) to pixel regions, e.g., a driving voltage line 146 b , a reference voltage line 147 b and a ground line 145 b may be formed in the active area (A/A).
[0055] A pixel (P) having a plurality of switching devices may be formed at the pixel region. The pixel (P) may operate by being connected to each of the gate line (GL), the data line (DL) and the sensing line (SL).
[0056] FIG. 5 is an equivalent circuit diagram for a single pixel in the flexible OLED display device of FIG. 4 .
[0057] Referring to FIGS. 4 and 5 , the pixel (P) in the active area (A/A) may have a structure where three switching devices (ST 1 , DT, ST 2 ), one capacitor (C) and one organic light emitting diode (OLED) are formed. However, the present invention is not limited to this configuration. That is, the pixel (P) may be formed to have various structures such as 2T1C, 4T1C, 5T1C and 6T1C.
[0058] The switching devices (ST 1 , DT, ST 2 ) may include a switching transistor (ST 1 ), a driving transistor (DT) and a sensing transistor (ST 2 ). The switching device (ST 1 , DT, ST 2 ) may be thin film transistors (TFT), for example, formed of amorphous silicon or poly-crystalline silicon.
[0059] The switching transistor (ST 1 ) of the pixel (P) may include a gate electrode connected to the gate line (GL) of the active area (A/A), a source electrode connected to the data line (DL), and a drain electrode connected to the driving transistor (DT). The switching transistor (ST 1 ) may output a data signal supplied from the data line (DL) to the driving transistor (DT), according to a gate signal supplied from the gate line (GL).
[0060] The driving transistor (DT) of the pixel (P) may include a gate electrode connected to the drain electrode of the switching transistor (ST 1 ), a source electrode connected to an OLED, and a drain electrode connected to driving voltage lines 146 a , 146 b for supplying a driving voltage (VDD). The driving transistor (DT) may control the size of current applied to the OLED from the driving voltage (VDD), according to a data signal supplied from the switching transistor (ST 1 ).
[0061] The capacitor (C) of the pixel (P) may be connected between the gate electrode of the driving transistor (DT) and the OLED. The capacitor (C) may store therein a voltage corresponding to a data signal supplied to the gate electrode of the driving transistor (DT). Also, the capacitor (C) may constantly maintain an ‘ON’ state of the driving transistor (DT) for a single frame, with the voltage stored therein.
[0062] The sensing transistor (ST 2 ) of the pixel (P) may include a gate electrode connected to the sensing line (SL), a source electrode connected to the source electrode of the driving transistor (DT), and a drain electrode connected to reference voltage lines 147 a , 147 b for supplying a reference voltage (Vref). The sensing transistor (ST 2 ) may sense a threshold voltage (Vth) of the driving transistor (DT), thereby preventing a malfunction of the OLED.
[0063] The switching transistor (ST 1 ) of the pixel (P) may be turned on by a gate signal supplied to the gate line (GL), and the capacitor (C) of the pixel (P) may be charged with charges by a data signal supplied to the data line (DL). The amount of current applied to the channel of the driving transistor (DT) may be determined according to a potential difference between a voltage charged at the capacitor (C) and the driving voltage (VDD). The amount of light emitted from the OLED may be determined based on such amount of current. As the OLED emits light, an image is displayed.
[0064] The sensing transistor (ST 2 ) may be turned on earlier than the switching transistor (ST 1 ), according to a sensing signal supplied through the sensing line (SL). Under such configuration, electroluminescence of the OLED by the driving voltage (EVDD), which occurs before a data signal is charged at the capacitor (C) during an initial operation of the switching transistor (ST 1 ), can be prevented.
[0065] Referring back to FIG. 4 , the non-active area (N/A) of the flexible OLED display device 100 may be formed adjacent, for example, around the active area (A/A). Driving circuitry for driving the pixels (P) in the active area (A/A) and wires may be formed in the non-active area (N/A).
[0066] The driving circuitry may include a data driving portion 230 , a gate driving portion 210 and a light-emitting controller 220 .
[0067] The data driving portion 230 may be mounted at the non-active area (N/A) below the active area (A/A), in the form of a chip. The data driving portion 230 may generate a data signal by receiving a signal from an external printed circuit board (not shown). The generated data signals may be output to the plurality of data lines (DL) in the active area (A/A) through wires.
[0068] The data driving portion 230 may output a gate signal and a light-emitting signal provided from external circuitry, to the gate driving portion 210 and the light-emitting controller 220 through wires, respectively. The data driving portion 230 may output power signals provided from external circuitry, e.g., power signals including a driving voltage (VDD), a reference voltage (Vref), a ground voltage (GND), etc., to driving voltage lines 146 a , 146 b , reference voltage lines 147 a , 147 b , and ground lines 145 a , 145 b , respectively.
[0069] The gate driving portion 210 may be formed at one side of the non-active area (N/A) outside the active area (A/A), in the form of a gate in panel (GIP). The gate driving portion 210 may sequentially output gate signals provided from the data driving portion 230 through wires (e.g., gate signal lines 141 a ), to the plurality of gate lines (GL) in the active area (A/A).
[0070] The light-emitting controller 220 may be formed at another side of the non-active area (N/A) outside the active area (A/A), in the form of a gate in panel (GIP) so as to correspond to the gate driving portion 210 . The light-emitting controller 220 may sequentially output light-emitting signals provided from the data driving portion 230 through wires (e.g., light-emitting lines 141 c ), to the plurality of sensing lines (SL) in the active area (A/A).
[0071] The wires may include power lines and signal lines formed between the data driving portion 230 and the active area (A/A). The power lines may include driving voltage lines 146 a , 146 b , reference voltage lines 147 a , 147 b , and ground lines 145 a , 145 b . Also, the signal lines may include a gate signal line 141 a , a data signal line 141 b , and a light-emitting signal line 141 c.
[0072] The power lines may supply power signals provided from the data driving portion 230 , to the active area (A/A). The signal lines may supply driving signals provided from the data driving portion 230 , e.g., a gate signal, a data signal and a light-emitting signal, to the active area (A/A), the gate driving portion 210 and the light-emitting controller 220 .
[0073] The driving voltage lines 146 a , 146 b may be formed in the lower end non-active area (N/A), and may output a driving voltage (VDD) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0074] The driving voltage lines 146 a , 146 b may include a first driving voltage line 146 a and a second driving voltage line 146 b . The first driving voltage line 146 a connected to the data driving portion 230 . The second driving voltage line 146 b may be connected to the first driving voltage line 146 a and formed as a bar in a direction parallel to the data driving portion 230 . The second driving voltage line 146 b may be formed such that one side thereof is connected to the first driving voltage line 146 a , and another side thereof is extending to the pixel (P) in the active area (A/A). Based on this configuration, the second driving voltage line 146 b may output a driving voltage (VDD) provided through the first driving voltage line 146 a to each pixel (P).
[0075] The reference voltage lines 147 a , 147 b may be formed in the lower end non-active area (N/A), and may output a reference voltage (Vref) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0076] The reference voltage lines 147 a , 147 b may include a first reference voltage line 147 a and a second reference voltage line 147 b . The first reference voltage line 147 a connected to the data driving portion 230 . The second reference voltage line 147 b may be connected to the first reference voltage line 147 a and formed as a bar in parallel to the second driving voltage line 146 b . The second reference voltage line 147 b may be formed such that one side thereof is connected to the first reference voltage line 147 a , and another side thereof is extending to the pixel (P) in the active area (A/A). Based on this configuration, the second reference voltage line 147 b may output a reference voltage (Vref) provided through the first reference voltage line 147 a to each pixel (P).
[0077] The ground lines 145 a , 145 b may be formed in the lower end non-active area (N/A), and may output a ground voltage (GND) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0078] The ground lines 145 a , 145 b may include a first ground line 145 a and a second ground line 145 b . The first ground line 145 a connected to the data driving portion 230 . The second ground line 145 b may be connected to the first ground line 145 a , and formed as a bar in parallel to the second driving voltage line 146 b and the second reference voltage line 147 b . The second ground line 145 b may be formed such that one side thereof is connected to the first ground line 145 a , and another side thereof is extending to the pixel (P) in the active area (A/A). By this configuration, the second ground line 145 b may output a ground voltage (GND) provided through the first ground line 145 a to each pixel (P).
[0079] The gate signal line 141 a may be formed between the data driving portion 230 and the gate driving portion 210 in the lower end non-active area (N/A). The gate signal line 141 a may output a gate signal provided from the data driving portion 230 to the gate driving portion 210 . The gate signal may be output to the plurality of gate lines (GL) in the active area (A/A), through the gate driving portion 210 .
[0080] The data signal line 141 b may be formed in the lower end non-active area (N/A), between the data driving portion 230 and the data line (DL) in the active area (A/A). The data signal line 141 b may output a data signal provided from the data driving portion 230 to the plurality of data lines (DL) in the active area (A/A).
[0081] The light-emitting signal line 141 c may be formed in the non-active area (N/A) between the data driving portion 230 and the light-emitting controller 220 . The light-emitting signal line 141 c may output a light-emitting signal provided from the data driving portion 230 , to the light-emitting controller 220 . The light-emitting signal may be output to the plurality of sensing lines (SL) in the active area (A/A), by the light-emitting controller 220 .
[0082] In the flexible OLED display device 100 according to this embodiment of the present invention, the lower end non-active area (N/A) may include a bending area (B/A). The bending area (B/A) may be a region which has a predetermined curvature when part of the lower end non-active area (N/A) is bent to the rear or front surface of the flexible OLED display device 100 . That is, the bending area (B/A) is a flexible portion including flexible materials that is provided between one end of the display device 100 and the other part of the device 100 and allows the one end to be bent or rotated around the bending area (B/A) toward the front or rear surface of the other part. In accordance with one embodiment, the lower end non-active area (N/A) may be bent around the bending area (B/A) toward the front or rear surface of the flexible OLED display device 100 . As an example, the lower end non-active area (N/A) may be attached to the rear surface of the flexible OLED display device 100 by the rotation around the bending area (B/A). Although FIG. 4 shows only one bending area formed adjacent one end of the flexible OLED display device 100 , it will be readily appreciable to one skilled in the art that the bending area (B/A) may be formed adjacent any side of the flexible OLED display device 100 (e.g. 4 bending areas formed adjacent 4 sides of the flexible OLED display device 100 in rectangular shape).
[0083] The lower end non-active area (N/A) may be divided into three regions by the bending area (B/A). For instance, the lower end non-active area (N/A) may be divided into a first area between the bending area (B/A) and the active area (A/A), the bending area (B/A), and a second area between the bending area (B/A) and an area where the data driving portion 230 has been mounted.
[0084] The first area of the lower end non-active area (N/A) may be a region covered by a bezel portion, etc., together with the rest of the non-active area (N/A). Also, the second area may be a region that may be positioned on a rear surface of the flexible OLED display device 100 , by bending of the bending area (B/A).
[0085] Power lines, which include the second driving voltage line 146 b , the second reference voltage line 147 b and the second ground line 145 b , may be formed in the first area of the lower end non-active area (N/A).
[0086] Signal lines, which include the gate signal line 141 a , the data signal line 141 b and the light-emitting signal line 141 c , may be formed in the first area so as to cross the power lines. The signal lines and the power lines in the first area may be formed to overlap each other at different layers on the flexible substrate 110 .
[0087] Power lines, which include the first driving voltage line 146 a , the first reference voltage line 147 a and the first ground line 145 a , may be formed in the bending area (B/A) of the lower end non-active area (N/A).
[0088] Signal lines, which include the gate signal line 141 a , the data signal line 141 b and the light-emitting signal line 141 c , may be formed in the bending area (B/A) in parallel to the power lines so as not to cross the power lines. The signal lines and the power lines in the bending area (B/A) may be formed to be spaced from each other on the same layer on the flexible substrate 110 .
[0089] The power lines, which include the first driving voltage line 146 a , the first reference voltage line 147 a and the first ground line 145 a , may be formed in the second area of the lower end non-active area (N/A).
[0090] The signal lines, which include the gate signal line 141 a , the data signal line 141 b and the light-emitting signal line 141 c , may be formed in the second area in parallel to the power lines so as not to cross the power lines. The signal lines and the power lines may be formed to be extending from the data driving portion 230 in parallel to each other. In this case, the signal lines and the power lines may be formed to be in parallel to each other by being bent at least twice in the second area. The signal lines and the power lines in the second area may be formed to be spaced from each other on the same layer.
[0091] As mentioned above, in the flexible OLED display device 100 according to this embodiment, wires are formed on the same layer in parallel to each other, in the bending area (B/A) of the lower end non-active area (N/A) where bending is performed. Accordingly, unlike in the conventional art, the occurrence of disconnection of the wires due to bending stress can be prevented.
[0092] In the second area and the bending area (B/A) of the lower end non-active area (N/A), wires are formed on the same layer. However, in the first area, wires are formed on different layers. By such configuration, wires formed in the bending area (B/A) may be connected to wires formed on different layers in the first area, through holes (not shown).
[0093] FIG. 6 is a cross-sectional view taken along line VIa˜VIa′ and VIb˜VIb′ in the flexible OLED device of FIG. 4 .
[0094] Referring to FIGS. 4 and 6 , the flexible OLED display device 100 may include pixels (P) formed in the active area (A/A), and wires formed in the non-active area (N/A) (e.g., lower end non-active area (N/A)). The lower end non-active area (N/A) where wires have been formed may be the bending area (B/A).
[0095] A thin film transistor (TFT) and an organic light emitting diode (OLED) may be formed on the flexible substrate 110 in the active area (A/A).
[0096] For instance, a passivation layer 111 may be formed on the entire surface of the flexible substrate 110 . A semiconductor layer 121 formed of amorphous or poly-crystalline silicon may be formed on the passivation layer 111 .
[0097] A gate insulating layer 113 may be formed on the semiconductor layer 121 , and a gate electrode 123 may be formed on the gate insulating layer 113 at a position corresponding to a predetermined region of the semiconductor layer 121 .
[0098] An interlayer insulating layer 115 may be formed on the gate electrode 123 , and a source electrode 125 a and a drain electrode 125 b may be formed on the interlayer insulating layer 115 .
[0099] The source electrode 125 a and the drain electrode 125 b may be connected to the semiconductor layer 121 , through contact holes (not shown) formed at the interlayer insulating layer 115 and the gate insulating layer 113 .
[0100] The semiconductor layer 121 , the gate electrode 123 , the source electrode 125 a and the drain electrode 125 b may constitute a thin film transistor in the active area (A/A) of the flexible substrate 110 . The TFT may be, for example, a driving transistor of the flexible OLED display device 100 . However, the present invention is not limited to this example.
[0101] A planarization layer 117 may be formed on the TFT. A first electrode 131 , connected to the drain electrode 125 b through a contact hole (not shown), may be formed on the planarization layer 117 .
[0102] A pixel defining layer 130 , through which part of the first electrode 131 is exposed to the outside, may be formed on the first electrode 131 . A light-emitting layer 133 may be formed on the pixel defining layer 130 . The light-emitting layer 133 may be formed on the first electrode 131 which has been exposed to the outside by the pixel defining layer 130 . A second electrode 135 may be formed on the light-emitting layer 133 .
[0103] The first electrode 131 , the light-emitting layer 133 and the second electrode 135 may constitute an OLED in the active area (A/A) of the flexible substrate 110 .
[0104] Signal lines and power lines may be formed on the flexible substrate 110 in the bending area (B/A). The signal lines may include the gate signal line 141 a and the data signal line 141 b . The power lines may include the first ground line 145 a and the first driving voltage line 146 a.
[0105] For instance, the passivation layer 111 may be formed on the entire surface of the flexible substrate 110 . The gate signal line 141 a , the data signal line 141 b , the first ground line 145 a and the first driving voltage line 146 a may be formed commonly on the passivation layer 111 , such that they are spaced from each other with a predetermined distance therebetween, for example, in parallel to each other.
[0106] In accordance with one embodiment, the signal lines and the power lines formed in the bending area (B/A) may be formed of the same metallic material as the source electrode 125 a and the drain electrode 125 b formed in the active area (A/A), at the same processing stage.
[0107] Like in the active area (A/A), the planarization layer 117 may be formed as an insulating layer on the signal lines and the power lines formed in the bending area (B/A).
[0108] As mentioned above, in the flexible OLED display device 100 according to one embodiment, wires may be formed on the same layer in the bending area (B/A), with the same metallic material. Accordingly, even if the planarization layer 117 is damaged by bending stress in the bending area (B/A), the wires in the bending area (B/A) are not disconnected or cracked. This can prevent a malfunction of the flexible OLED display device 100 .
[0109] FIGS. 7A to 7C are views illustrating processes of fabricating a flexible OLED display device according to the first embodiment of the present invention.
[0110] A passivation layer 111 may be formed on the entire surface of a substrate divided into an active area (A/A) and a non-active area (N/A), e.g., a glass substrate 101 . The passivation layer 111 is provided so that thin film transistors, organic light-emitting diodes and wires can be prevented from being damaged during the process of detaching the glass substrate 101 , as described below in more detail.
[0111] The non-active area (N/A) may include a bending area (B/A) formed below the active area (A/A), i.e., a bending area (B/A) of a lower end non-active area (N/A).
[0112] Amorphous silicon or poly-crystalline silicon is deposited in the active area (A/A) on the glass substrate 101 where the passivation layer 111 has been formed. Then the amorphous silicon or the poly-crystalline silicon is selectively patterned, thereby forming a semiconductor layer 121 . The semiconductor layer 121 may include a source region and a drain region each including impurities, and a channel region including no impurities.
[0113] A gate insulating layer 113 may be formed on the entire surface of the glass substrate 101 where the semiconductor layer 121 has been formed. The gate insulating layer 113 may be formed as a silicon oxide film (SiOx), a silicon nitride film (SiNx), or a multi-layer thereof.
[0114] The gate insulating layer 113 may not be formed in the non-active area (N/A) of the glass substrate 101 .
[0115] A gate electrode 123 may be formed on the gate insulating layer 113 , at a position corresponding to a channel region of the semiconductor layer 121 . The gate electrode 123 may be formed by depositing a metallic material such as molybdenum (Mo), aluminum (Al), chrome (Cr), titanium (Ti) and copper (Cu), or an alloy thereof, on the gate insulating layer 113 , and then by selectively patterning the metallic material or the alloy.
[0116] An interlayer insulating layer 115 may be formed on the entire surface of the active area (A/A) of the glass substrate 101 where the gate electrode 123 has been formed. The interlayer insulating layer 115 may be formed as a silicon oxide film (SiOx), a silicon nitride film (SiNx), or a multi-layer thereof.
[0117] Contact holes (not shown) may be formed by etching part of the interlayer insulating layer 115 and the gate insulating layer 113 , thereby exposing part of the semiconductor layer 121 , e.g., a source region and a drain region to the outside therethrough.
[0118] A source electrode 125 a and a drain electrode 125 b may be formed on the interlayer insulating layer 115 . The source electrode 125 a may be formed so as to be connected to the source region of the semiconductor layer 121 through the contact hole, and the drain electrode 125 b may be formed so as to be connected to the drain region of the semiconductor layer 121 through the contact hole.
[0119] The source electrode 125 a and the drain electrode 125 b may be formed by depositing a metallic material such as Ti, Al and Mo, or an alloy thereof such as Ti/Al/Ti and Mo/Al, on the interlayer insulating layer 115 , and then by selectively patterning the metallic material or the alloy.
[0120] A thin film transistor (TFT) including the semiconductor layer 121 , the gate electrode 123 , the source electrode 125 a and the drain electrode 125 b , which is, e.g., a driving transistor of the flexible OLED display device 100 , may be formed in the active area (A/A) of the glass substrate 101 .
[0121] Wires, e.g., a gate signal line 141 a , a data signal line 141 b , a first ground line 145 a and a first driving voltage line 146 a may be formed on the passivation layer 111 , in the non-active area (N/A) of the glass substrate 101 . Such wires may be formed on the passivation layer 111 so as to be spaced from each other with a predetermined interval.
[0122] The gate signal line 141 a , the data signal line 141 b , the first ground line 145 a and the first driving voltage line 146 a may be formed of the same metallic material as the source electrode 125 a and the drain electrode 125 b , at the same processing stage.
[0123] Referring to FIG. 7B , a planarization layer 117 may be formed on the entire surface of the active area (A/A) where a thin film transistor has been formed, and the non-active area (N/A) where wires have been formed.
[0124] The planarization layer 117 may be formed by a spin coating method, for example, the method for coating an organic material or an inorganic material such as polyimide, benzocyclobutene series resin and acrylate, in the form of a liquid phase, and then hardening the material.
[0125] A contact hole (not shown) may be formed by etching part of the planarization layer 117 in the active area (A/A), thereby exposing the drain electrode 125 b to the outside therethrough.
[0126] A first electrode 131 may be formed on the planarization layer 117 in the active area (A/A). The first electrode 131 may be connected to the drain electrode 125 b through the contact hole of the planarization layer 117 .
[0127] The first electrode 131 may be formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) or ZnO (Zinc Oxide), which may form the anode of an OLED.
[0128] A pixel defining layer 130 may be formed on the first electrode 131 . The pixel defining layer 130 may have an opening through which part of the first electrode 131 is exposed to the outside, and may define a pixel region.
[0129] The pixel defining layer 130 may be formed by a spin coating method, for example, the method for coating an organic material or an inorganic material such as polyimide, benzocyclobutene series resin and acrylate, in the form of a liquid phase, and then hardening the material.
[0130] Referring to FIGS. 7B and 7C , a light-emitting layer 133 may be formed on the pixel defining layer 130 . The light-emitting layer 133 may be formed on the opening of the pixel defining layer 130 , i.e., may be formed on the first electrode 131 exposed to the outside by the pixel defining layer 130 .
[0131] A second electrode 135 may be formed on the light-emitting layer 133 . The second electrode 135 may be formed of aluminum (Al), silver (Ag), magnesium (Mg), or an alloy thereof by deposition.
[0132] An OLED including the first electrode 131 , the light-emitting layer 133 and the second electrode 135 may be formed on a TFT of the glass substrate 101 in the active area (A/A).
[0133] When a TFT and an OLED have been formed in the active area (A/A) and wires have been formed in the non-active area (N/A), the glass substrate 101 may be detached from the passivation layer 111 . Then, a flexible substrate 110 may be attached to the passivation layer 111 .
[0134] The flexible substrate 110 may have the same active area (A/A) and non-active area (N/A) as the glass substrate 101 .
[0135] The flexible substrate 110 may be formed, for example, of one of polycarbon, polyimide, polyether sulfone (PES), polyarylate, polyethylene naphthalate (PEN) or poly ethyleneterephthalate (PET).
[0136] The glass substrate 101 may be detached from the passivation layer 111 through irradiation of laser, etc., and the flexible substrate 110 may be attached to the passivation layer 111 by an adhesive tape such as an optically clear adhesive (OCA), with reference to FIG. 7C .
[0137] FIG. 8 is a planar view of a flexible OLED display device according to a second embodiment of the present invention.
[0138] Referring to FIG. 8 , the flexible OLED display device according to the second embodiment may be formed on a flexible substrate 110 having an active area (A/A) and a non-active area (N/A).
[0139] The active area (A/A) is a region where an image is substantially displayed. On the active area (A/A), a plurality of gate lines (GL) and a plurality of data lines (DL) may be formed to cross each other, thereby defining pixel regions. A plurality of sensing lines (SL) may be formed in parallel to the plurality of gate lines (GL).
[0140] Power lines for supplying a driving voltage (VDD), a reference voltage (Vref) and a ground voltage (GND) to pixel regions, e.g., a driving voltage line 146 b , a reference voltage line 147 b and a ground line 145 b may be formed in the active area (A/A).
[0141] A pixel (P) having a plurality of switching devices may be formed at the pixel region. The pixel (P) may be the same pixel as described above with reference to FIG. 5 .
[0142] The non-active area (N/A) of the flexible OLED display device 200 may be formed around the active area (A/A), which may be defined by the dotted line. Driving circuitry for driving the pixels (P) in the active area (A/A) and wires may be formed in the non-active area (N/A).
[0143] The driving circuitry may include a data driving portion 230 , a gate driving portion 210 and a light-emitting controller 220 .
[0144] The data driving portion 230 may be mounted in the non-active area (N/A) positioned below the active area (A/A), i.e., the lower-end non-active area (N/A). The gate driving portion 210 and the light-emitting controller 220 may be formed in the non-active area (N/A), i.e., at two sides outside the active area (A/A), in the form of a gate in panel (GIP).
[0145] The data driving portion 230 may generate a data signal by receiving a signal from an external circuit. The generated data signal may be output to the plurality of data lines (DL) in the active area (A/A) through wires. The gate driving portion 210 may output a gate signal provided from the data driving portion 230 , to the plurality of gate lines (GL) in the active area (A/A), through wires. The light-emitting controller 220 may output a light-emitting signal provided from the data driving portion 230 , to the plurality of sensing lines (SL) in the active area (A/A), through wires.
[0146] Wires may include power lines including driving voltage lines 146 a , 146 b , reference voltage lines 147 a , 147 b , and ground lines 145 a , 145 b , and signal lines including a gate signal line 141 a , a data signal line 141 b , and a light-emitting signal line 141 c.
[0147] The driving voltage lines 146 a , 146 b may be formed in the lower end non-active area (N/A), and may output a driving voltage (VDD) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0148] The driving voltage lines 146 a , 146 b may include a first driving voltage line 146 a and a second driving voltage line 146 b . The first driving voltage line 146 a connected to the data driving portion 230 . The second driving voltage line 146 b may be connected to the first driving voltage line 146 a , and formed as a bar in a direction parallel to the data driving portion 230 . The second driving voltage line 146 b may be formed such that one side thereof is connected to the first driving voltage line 146 a , and another side thereof is extending to the pixel (P) in the active area (A/A). Based on this configuration, the second driving voltage line 146 b may output a driving voltage (VDD) provided through the first driving voltage line 146 a to each pixel (P).
[0149] The reference voltage lines 147 a , 147 b may be formed in the lower end non-active area (N/A), and may output a reference voltage (Vref) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0150] The reference voltage lines 147 a , 147 b may include a first reference voltage line 147 a and a second reference voltage line 147 b . The first reference voltage line 147 a connected to the data driving portion 230 . The second reference voltage line 147 b may be connected to the first reference voltage line 147 a , and formed as a bar in parallel to the second driving voltage line 146 b . The second reference voltage line 147 b may be formed such that one side thereof is connected to the first reference voltage line 147 a , and another side thereof is extending to the pixel (P) in the active area (A/A). Based on this configuration, the second reference voltage line 147 b may output a reference voltage (Vref) provided through the first reference voltage line 147 a to each pixel (P).
[0151] The ground lines 145 a , 145 b may be formed in the lower end non-active area (N/A), and may output a ground voltage (GND) provided from the data driving portion 230 to the pixel (P) in the active area (A/A).
[0152] The ground lines 145 a , 145 b may include a first ground line 145 a and a second ground line 145 b . The first ground line 145 a may be connected to the data driving portion 230 . Further, the second ground line 145 b may be connected to the first ground line 145 a , and formed as a bar in a direction parallel to the second driving voltage line 146 b and the second reference voltage line 147 b . The second ground line 145 b may be formed such that one side thereof is connected to the first ground line 145 a , and another side thereof is extending to the pixel (P) in the active area (A/A). Based on this configuration, the second ground line 145 b may output a ground voltage (GND) provided through the first ground line 145 a to each pixel (P).
[0153] The gate signal line 141 a may be formed in the lower end non-active area (N/A), between the data driving portion 230 and the gate driving portion 210 . The gate signal line 141 a may output a gate signal provided from the data driving portion 230 to the gate driving portion 210 . The gate signal may be output to the plurality of gate lines (GL) in the active area (A/A), through the gate driving portion 210 .
[0154] The data signal line 141 b may be formed in the lower end non-active area (N/A), between the data driving portion 230 and the data line (DL) in the active area (A/A). The data signal lines 141 b may output data signals provided from the data driving portion 230 to the plurality of data lines (DL) in the active area (A/A).
[0155] The light-emitting signal line 141 c may be formed in the non-active area (N/A), between the data driving portion 230 and the light-emitting controller 220 . The light-emitting signal line 141 c may output a light-emitting signal provided from the data driving portion 230 , to the light-emitting controller 220 . The light-emitting signal may be output to the plurality of sensing lines (SL) in the active area (A/A), by the light-emitting controller 220 .
[0156] In the flexible OLED display device 200 according to the second embodiment of the present invention, the lower end non-active area (N/A) may include a bending area (B/A). The bending area (B/A) may be a region which has a predetermined curvature when part of the lower end non-active area (N/A) is bent to the front or rear surface of the flexible OLED display device 200 .
[0157] The lower end non-active area (N/A) may be divided, for example, into three regions by the bending area (B/A). For instance, the lower end non-active area (N/A) may be divided into a first area between the bending area (B/A) and the active area (A/A), the bending area (B/A), and a second area between the bending area (B/A) and an area where the data driving portion 230 has been mounted.
[0158] The first area of the lower end non-active area (N/A) may be a region covered by a bezel portion, etc., together with the rest of the non-active area (N/A). Also, the second area may be a region positioned on the rear surface of the flexible OLED display device 200 , by bending of the bending area (B/A).
[0159] The plurality of data signal lines 141 b and the plurality of power lines may be formed in the first area. The plurality of power lines include the second driving voltage line 146 b , the second reference voltage line 147 b and the second ground line 145 b . The plurality of data signal lines 141 b may be connected to the plurality of data lines (DL) in the active area (A/A). The plurality of data signal lines 141 b and the plurality of power lines may be formed in the first area in parallel with each other.
[0160] In the bending area (B/A) of the lower end non-active area (N/A), the plurality of data signal lines 141 b and the plurality of power lines formed in the first area, may be formed in parallel with each other.
[0161] In the bending area (B/A) of the lower end non-active area (N/A), the plurality of lines extending from the power lines toward the active area (A/A), the plurality of data signal lines 141 b , the gate signal lines 141 a and the light-emitting signal lines 141 c may be formed so as to be spaced from each other on the same layer on the flexible substrate 110 .
[0162] In the second area of the lower-end non-active area (N/A), signal lines including the gate signal lines 141 a , the data signal lines 141 b and the light-emitting signal lines 141 c may be formed to cross power lines. The power lines, which may have a bar shape, may include first and second driving voltage lines 146 a , 146 b , first and second reference voltage lines 147 a , 147 b , and first and second ground lines 145 a , 145 b . The signal lines and the power lines in the second area may be formed to overlap each other on different layers on the flexible substrate 110 .
[0163] The signal lines and the power lines may be formed to be in parallel to each other in the first area and the bending area (B/A), by being bent at least twice in the second area.
[0164] That is, in the flexible OLED display device 200 according to the second embodiment, a plurality of signal lines and a plurality of power lines may be formed to cross each other in the second area positioned on the rear surface of the flexible OLED display device 200 when the bending area (B/A) of the lower end non-active area (N/A) is bent toward the rear surface of the device 200 . Thus, in the flexible OLED display device 200 according to the second embodiment, the width of the lower end non-active area (N/A) can be more reduced than in the conventional flexible OLED display device. As a result, the flexible OLED display device 200 according to the second embodiment can have a narrow bezel portion.
[0165] As mentioned above, in the flexible OLED display device 200 according to the second embodiment, a plurality of signal lines and a plurality of power lines are formed on the same layer in parallel to each other, in the bending area (B/A) of the lower end non-active area (N/A). Accordingly, unlike in the conventional art, disconnection of the wires can be prevented even if an insulating layer is damaged due to bending stress.
[0166] In the first area and the bending area (B/A) of the lower end non-active area (N/A), wires are formed on the same layer in accordance with one embodiment of the invention. However, in the second area, wires may be formed on different layers. Based on this configuration, wires formed on different layers in the second area may be connected to wires formed on the same layer in the bending area (B/A), through holes (not shown).
[0167] FIG. 9 is a cross-sectional view taken along line in the flexible OLED display device of FIG. 8 .
[0168] Referring to FIGS. 8 and 9 , in the bending area (B/A) of the lower end non-active area (N/A) of the flexible OLED display device 200 , a plurality of wires may be formed on the same layer in a spaced manner from each other.
[0169] For instance, in the bending area (B/A), a passivation layer 111 is formed on a flexible substrate 110 . A gate signal line 141 a , a data signal line 141 b , a second ground line 145 b and a second driving voltage line 146 b may be formed on the passivation layer 111 , such that they are spaced from each other with predetermined distances, in parallel to each other.
[0170] A first insulating layer 117 a may be formed on the gate signal line 141 a , the data signal line 141 b , the second ground line 145 b and the second driving voltage line 146 b.
[0171] A plurality of wires may be formed to overlap each other on different layers, in the second area positioned on the rear surface of the flexible OLED display device 200 when the bending area (B/A) of the lower end non-active area (N/A) is bent.
[0172] For instance, in the second area, a passivation layer 111 is formed on a flexible substrate 110 . A gate signal line 141 a and a data signal line 141 b may be formed on the passivation layer 111 , such that they are spaced from each other in parallel to each other.
[0173] A first insulating layer 117 a may be formed on the gate signal line 141 a and the data signal line 141 b . A second ground line 145 b and a second driving voltage line 146 b may be formed on the first insulating layer 117 a , with a predetermined distance therebetween in parallel to each other. In this case, the second ground line 145 b and the second driving voltage line 146 b may be formed to overlap the gate signal line 141 a and the data signal line 141 b.
[0174] A second insulating layer 117 b may be formed on the second ground line 145 b and the second driving voltage line 146 b.
[0175] In the flexible OLED display device 200 according to the second embodiment, the pixel region in the active area (A/A) has the same cross-sectional profile as the pixel region described above with reference to FIG. 6 , of which description is not repeated.
[0176] A plurality of wires formed in the non-active area (N/A) may be formed of the same metallic material as a source electrode (not shown) and a drain electrode (not shown) in the pixel region, at the same processing stage. The plurality of wires indicate power lines including the second ground line 145 b and the second driving voltage line 146 b , and signal lines including the gate signal line 141 a and the data signal line 141 b . For instance, the plurality of wires may be formed of a metallic material such as Ti, Al and Mo or an alloy thereof such as Ti/Al/Ti and Mo/Al.
[0177] FIG. 10 is a view illustrating a wire structure in a bending area in a flexible OLED display device according to the present invention, and FIG. 11 is a view illustrating various embodiments of FIG. 10 .
[0178] In this embodiment, the flexible OLED display device 100 of FIG. 4 will be explained for convenience. However, this embodiment may be also applicable to the flexible OLED display device 200 of FIG. 8 .
[0179] Referring to FIGS. 4 and 10 , in the flexible OLED display device 100 , wires may be formed to have a large width for prevention of disconnection thereof due to bending stress in the bending area (B/A) of the lower end non-active area (N/A).
[0180] For instance, as shown in FIG. 10 , the width (d 2 ) of wires in the bending area (B/A) of the lower end non-active area (N/A) may be greater than the width (d 1 ) of wires in the first area and the second area of the lower end non-active area (N/A).
[0181] As shown in FIG. 11 , wires are formed, in the bending area (B/A), with a shape such as a triangle, a diamond, a semi-circle and a circle. Thus, disconnection of the wires, due to bending stress occurring when the bending area (B/A) is bent, can be prevented.
[0182] That is, in the flexible OLED display device 100 , disconnection of wires, which occurs when the bending area (B/A) is bent, can be prevented by various shape changes of the wires in the bending area (B/A). In order to prevent resistance increase of the wires due to the shape changes of the wires, the wires may be formed such that the width in the bending area (B/A) is larger than that in the other regions. As a result, disconnection of the wires, which occurs when the bending area (B/A) is bent, can be prevented.
[0183] The aforementioned wires may be power lines including the first ground line 145 a and the first driving voltage line 146 a , and signal lines including the gate signal line 141 a and the data signal line 141 b.
[0184] The foregoing embodiments and advantages are merely exemplary and are not to be considered as limiting the present disclosure. The present teachings can be readily applied to other types of apparatuses. This description is intended to be illustrative, and not to limit the scope of the claims. Many alternatives, modifications, and variations will be apparent to those skilled in the art. The features, structures, methods, and other characteristics of the exemplary embodiments described herein may be combined in various ways to obtain additional and/or alternative exemplary embodiments.
[0185] As the present features may be embodied in several forms without departing from the characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be considered broadly within its scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalents of such metes and bounds are therefore intended to be embraced by the appended claims.
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A display device includes a first substrate including an active area, a bending area, and a pad area; a plurality of pixels to display an image in the active area, each of the plurality of pixels including an organic light emitting diode (OLED); a signal line and a power line disposed on the first substrate, the signal line and the power ling being disposed on a same layer in the bending area, the bending area on the first substrate being configured to be bent flexibly; and a second substrate facing the active area and disposed on the first substrate.
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This application is a continuation of application Ser. No. 07/766,632 filed Sep. 26, 1991, which is a continuation of application Ser. No. 07/578,761 filed Sep. 6, 1990, now U.S. Pat. No. 5,061,122.
BACKGROUND OF THE INVENTION
The present invention relates generally to modular caissons which can be assembled in different configurations to form wave defense systems in deep or shallow waters, and more particularly to standardized, modular caissons which are constructed onshore in the form of either monolithic caissons or caisson sub-assemblies which are assembled on site to form caissons, floated to a preselected site, trimmed and ballasted down to form a wave defense system.
In large, open bodies of water, the forces generated by maximum force winds and waves can vary greatly depending on the location of, and underlying conditions at, any particular site. Because of this great variation, it has heretofore not been possible to standardize the design of wave defense systems to any appreciable extent. Instead, wave defense systems have generally been designed as one-of-a-kind structures suited to the requirements of a particular site. This results in construction being undertaken at a location near or at the site in question, with little, if any, cost savings being available from standardized production methods, such as those available in shipyards and shipyard-type facilities.
Usual wave defense systems include breakwaters, groins, pilings, caissons and the like.
Caissons are typically constructed of concrete and/or steel and may be of either the floating or sunken type. A floating caisson floats on the surface and is anchored to the seabed, lake bed, etc. A sunken caisson, on the other hand, rests directly on the bed and may, depending on its construction, penetrate into the bed to aid in embedding the caisson in place.
Floating caissons present a danger of breaking loose in severe wind and wave conditions, such as during a hurricane or typhoon, regardless of how strongly the caissons are anchored. This is an extremely dangerous condition and results in a breach of the wave defense system which, in turn, destroys the integrity of the protected area behind the caissons. Similarly, sunken caissons, even though large enough to rest on, or even penetrate, the bed, also present a danger of breaking loose due to their hydrodynamic characteristics. For example, when severe storm waves and winds slam into the seaward side of a sunken caisson, the wind and wave forces create: a lifting force tending to lift the caisson off the bed; a turning moment tending to overturn the caisson; and a slamming force tending to move the caisson sideways--any of which, if large enough in magnitude, can lead to a caisson breaking loose thus resulting in a breach of the wave defense system.
By way of example, French Patent No. 1,012,795 dated Apr. 23, 1952 to Pascal Hermes discloses a sea wall made of sunken caissons. However, the caissons all have a greater height than width and are, therefore, likely to be toppled over when subjected to anything approaching maximum level wave and wind attack. This presents a serious drawback and severely restricts use of the sea wall to relatively shallow, protected waters. Another drawback is that the caissons appear to rest more or less on the surface of the seabed, with hardly any penetration into the bed, and thus are likely to be swept away by high waves. The caissons are not strongly anchored to the seabed and are not designed for use in deep, open waters subjected to severe wind and wave conditions. A further drawback is that the caissons have no additional use, other than their wave defense functions, so that their cost cannot be offset in any way other than by their wave defense function, i.e., the caissons have no revenue-earning capability. Another drawback is that the caissons are designed to be ballasted down but not ballasted up so that the caissons, once sunk into position, become a permanent structure. As a consequence, the caissons cannot be realigned or replaced and cannot be ballasted up and towed away for use at other locations, or for breakup in the event the sea wall has to be dismantled for environmental or other reasons. Because of these and other drawbacks, it is not believed that any sea wall using the caissons described in this patent has been built anywhere in the world.
Out in open waters, especially in deep water, breakwaters armored with riprap, concrete blocks, tetrapods, dolos, etc. represent the only viable method of constructing wave defense systems. At such locations, however, the cost becomes too high and constitutes a strong financial deterrent preventing the construction of breakwaters, especially in deeper, open waters which are exposed to maximum force winds and waves.
In addition, the problem of the extreme cost of constructing breakwaters and the like in deeper, open waters is compounded by the fact that such wave defense systems offer no additional economic benefits other than their value as a wave defense system. In short, the benefit/cost ratios of conventional wave defense systems are too low to justify their construction in open, deeper waters.
Another problem of using breakwaters as wave defense systems is that once the breakwater is breached, there generally is no second line of wave defense. Thus the area that had been protected by the wave defense system is open to the full force of wind and wave attack.
A further problem of constructing breakwaters massive enough to withstand severe hydrodynamic environments is that such breakwaters represent a large and permanent environmental "footprint" on the ocean floor, especially when the "core" thereof is made of dredged material. Due to their size, these breakwaters cannot be economically de-mounted and removed following the end of their useful life.
For the foregoing reasons, very few such wave defense systems have been actually constructed, for example, at deep water sites in the open ocean.
Further, those wave defense systems, such as breakwaters, that have been constructed in deeper, exposed waters cannot be built high enough, due to the prohibitive cost, to prevent wave over-topping, nor can they provide adequate protection on their lee sides from maximum strength winds. As a result, such wave defense systems do not provide adequate shelter on their lee sides for anchoring, docking or mooring vessels, especially when such wave defense systems are under maximum wind and wave attack. These conditions present a major problem for all vessels maneuvering at slow speed, or docking, or at anchor, especially vessels that have a high windage profile, such as container ships, cruise ships, tankers and bulk carriers, car carriers, and especially liquified gas carriers, such as LNG tankers and the like.
There are no known wave defense systems which can provide adequate shelter at deep water sites, as for example in the open ocean, when subjected to maximum wind and wave attack such as exists along, and off, the open coastlines surrounding the Atlantic, Pacific and Indian Oceans, for all classes of sea-going vessels engaged in commerce throughout the world.
Further complicating the construction of wave defense systems in large, open bodies of water such as the open ocean is the growing need to build any such system so that, at least from an environmental or navigational standpoint, it can be de-mounted and removed following the end of its useful life, thereby returning the ocean to, or as close as possible to, its pre-construction state.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a wave defense system that overcomes the aforementioned problems associated with the prior art systems.
Another object of the present invention is to provide a universal wave defense system that can protect any coastline or shoreline against beach erosion, or any artificial manmade island, against any level of wave and wind attack, including those arising from maximum scale hurricanes, typhoons, cyclones and tsunamis.
A further object of the present invention is to provide a wave defense system capable of withstanding maximum force winds and waves generated at the site of the wave defense system.
Another object of the present invention is to provide a wave defense system which is economically and technically feasible and which is environmentally benign.
Another object of the present invention is to provide a wave defense system comprised of ballastable, trimmable, modular caissons which are designed and assembled to withstand maximum wind and wave attack in open, deeper waters and which can be easily scaled down for use in calmer, shallower waters.
Another object of the present invention is to provide a wave defense system in large, open bodies of water (including the open ocean) at depths usually ranging from 20 to 100 feet, although, under certain conditions, depths up to 150 feet may be considered.
A further object of the present invention is to provide a wave defense system comprised of a plurality of primary, ballastable, modular caissons that can be constructed under cost-controlled conditions in shipyards, floated and towed out to a desired site, precisely trimmed, and then ballasted down and assembled into position to form an integrated wave defense system.
Yet another object of the present invention is to provide a wave defense system comprised of ballastable, modular caissons which can be ballasted down to form an integrated wave defense system and which can, if desired, be ballasted up and towed away at the end of the useful life of the wave defense system to enable the site to be restored as closely as possible to its pre-construction state.
A further object of the present invention is to provide a set of primary, ballastable, trimmable, modular caissons of different configurations which can be assembled in different combinations to constitute a wide array of wave defense systems and which can be scaled to size for use at different preselected sites having different water depths and different maximum wind and wave conditions.
A still further object of the present invention is to provide a modular caisson system comprised of a given number of standardized, ballastable caissons which can be scaled to different sizes and which can be deployed in a multitude of different configurations to form wave defense systems under different site conditions.
A further object of the present invention is to provide a wave defense system having a line of outer wave defense caissons and having, depending on site conditions, a reinforcement sub-system which is integral with the outer wave defense caissons and which acts as a reinforcing support system for supporting the line of outer wave defense caissons and which comprises a series of transverse support caissons and inner wave defense and multi-purpose caissons.
Another object of the present invention is to provide a wave defense system having a line of outer wave defense caissons and having, depending on site conditions, a wave over-topping absorption, containment and dispersion sub-system which is integral with the outer wave defense caissons and which is comprised of transverse support caissons and inner wave defense caissions for absorbing, containing and dispersing the energy of waves over-topping the line of outer wave defense caissons.
These as well as other objects, features and advantages of the invention are attained by providing a plurality of primary, ballastable, modular caissons of different configurations which can be assembled in different combinations to form a wide array of wave defense systems and which can be scaled to size for use at different preselected sites having different depths and subjected to different maximum force winds and waves. The primary, ballastable, modular caissons comprise anchor tower caissons, outer wave defense caissons, transverse support caissons, inner wave defense caissons, and multipurpose caissons.
The outer wave defense caissons are designed to be assembled in end-to-end relation to form a line which is anchored at one or both ends by an anchor tower caisson. A reinforcement sub-system may be provided for reinforcing the line of outer wave defense caissons, the reinforcement sub-system comprising one or more lines of inner wave defense caissons and multi-purpose caissons disposed on the leeward side of the line of outer wave defense caissons and integrated therewith through a series of transverse support caissons. In deep, open bodies of water, a wave overtopping absorption, containment and dispersion sub-system may be provided for absorbing, containing and dispersing the energy of waves over-topping the line of outer wave defense caissons. All of the primary, ballastable, modular caissons are designed to be constructed onshore in shipyard-type facilities, and then floated to the desired site, trimmed and ballasted down to form the integrated wave defense system.
The foregoing as well as other objects, features and advantages of the invention will become apparent to those of ordinary skill in the art upon a reading of the following detailed description of the invention when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an explanatory plan view showing one exemplary embodiment of a sea defense system constructed according to the principles of the present invention;
FIG. 2 is an explanatory plan view of another exemplary embodiment of a sea defense system constructed according to the principles of the present invention;
FIG. 3 is an explanatory plan view of a further exemplary embodiment of a sea defense system constructed according to the principles of the present invention;
FIG. 4 is an explanatory perspective view, partly in section, showing the assembly of wave defense caissons and storage caissons;
FIG. 5 is a perspective view showing the assembly of an anchor tower caisson and wave defense caissons;
FIG. 6 an explanatory cross-sectional view for use in explaining the construction of a sea defense system according to the principles of the present invention;
FIG. 7 is an explanatory cross-sectional view for use in explaining the construction of a sea defense system according to the principles of the present invention;
FIGS. 8a-8g are side elevations of standardized, primary, ballastable modular caissons which constitute the modular caisson system of the present invention;
FIGS. 8h-8k are explanatory side elevations for use in explaining the design principles of the outer wave defense caissons according to the present invention;
FIGS. 8l-8m are side elevations of variants of the anchor tower caisson shown in FIG. 8b;
FIG. 9 is a cross-sectional view of a representative embodiment of an integrated wave defense system at a deep water site;
FIG. 10a is a side elevation, partly in cross section, and FIG. 10b is a top plan of a typical wave defense system under minimum site conditions and at a minimum commercial depth;
FIG. 11a is a side elevation, partly in cross section, and FIG. 11b is a top plan of a typical wave defense system under intermediate site conditions and at an intermediate commercial depth;
FIG. 12a is a side elevation, partly in cross section, and FIG. 12b is a top plan of a typical wave defense system under maximum site conditions and at a maximum commercial depth.
FIGS. 13a-13c are explanatory side elevational views, partly in cross section, of typical integrated wave defense systems in shallower, more protected waters under varying hydrodynamic and site conditions;
FIG. 14 shows cross-sectional side elevations, at the same scale, of one type of standardized, ballastable modular caisson showing the size variation thereof across the full range of hydrodynamic and site conditions;
FIG. 15 is an explanatory cross-sectional view of a wave defense system designed for maximum hydrodynamic and site conditions for use in explaining the toppling factor; and
FIGS. 16a-16b are explanatory side views of two anchor tower caissons of different heights for use in explaining the penetration factor.
DETAILED DESCRIPTION OF THE INVENTION
To facilitate understanding of the modular caisson concept utilized in the present invention, a brief general description will be given of several illustrative wave defense systems constructed of modular caissons according to the invention followed by a description of representative standardized, primary, modular caissons which make up the modular caisson system. It is understood that the several illustrative embodiments of wave defense systems are merely representative of the multitude of different wave defense systems that can be constructed according to the principles of the present invention and that the invention is in no way limited or restricted to the particular configuration of wave defense systems illustrated in the drawings.
As used throughout the specification and claims, the term "wave defense system" refers to and means a system used in waters of any type, such as oceans, seas, bays, rivers, lakes, estuaries and the like. A wave defense system used in the ocean or sea is sometimes referred to as a "sea defense system". The protected, sheltered area on the leeward side of a wave defense system, or enclosed or partly enclosed by a wave defense system, is referred to as a "manmade island" because it is surrounded or substantially surrounded by relatively unprotected water. In other words, the protected area is a manmade refuge surrounded by unprotected water. The protected area may be filled, or partly filled, with sand, rock, gravel or other fill material to constitute a land island, or the protected area may remain filled with water to constitute a water island.
The term "primary" caisson refers to and means a ballastable, modular caisson which functions as a structural module in the integrated modular wave defense system. A primary caisson may, in addition, be designed to perform other functions, such as material processing, material storage, wave energy dissipation, etc. By contrast, a "secondary" caisson is one which functions in a capacity other than as a structural module in the integrated modular wave defense system.
General Description of Illustrative Wave Defense Systems Using Modular Caissons
One embodiment of a wave defense system constructed of ballastable, modular caissons according to the present invention is shown in FIG. 1, which is an explanatory plan view of a wave defense system constructed at a preselected ocean site in the open ocean. As the wave defense system in this embodiment is in the ocean, it will be referred to as a sea defense system. The sea defense system is comprised of a main line of outer wave defense caissons 10 which, as described hereinafter, are secured in place on the ocean floor and project above the ocean surface. The wave defense caissons 10 are positioned in end-to-end relation, and any number of caissons 10 may be used depending on the desired size of the protected area and the scale of the maximum wind and wave forces generated at the selected site. An anchor tower caisson 12 is positioned at the end of each of the endmost caissons 10 in the main line of wave defense caissons.
The anchor tower caissons 12 are securely embedded in the ocean floor and anchor the line of outer wave defense caissons 10 to form an integrated wave defense system. In this embodiment, the upper parts of the anchor tower caissons 12 extend above the level of the ocean surface.
In the embodiment shown in FIG. 1, the wave defense caissons 10 are arranged in a line which preferably curves outwardly in the direction of the prevailing winds and waves, thereby creating a manmade island in the form of a protected area A on the leeward side of the line of caissons. To further enclose and shelter the protected area A, secondary lines of wave defense caissons 10a are connected to the anchor tower caissons 12 and extend transversely thereof in the leeward direction. Additional anchor tower caissons 12a are connected to the ends of the endmost wave defense caissons 10a and, as a further measure of protection, additional wave defense caissons 10b are connected to the anchor tower caissons 12a.
As shown in FIG. 1, the outwardly curved main line of outer wave defense caissons 10 defines, relative to the oncoming winds and waves, an arch structure which is anchored at both ends by the corner anchor tower caissons 12. In accordance with classic "arch theory", such an arch-shaped arrangement of outer wave defense caissons 10 can withstand much greater wind and wave forces than would otherwise be possible if the caissons 10 were arranged in a straight line. The integrity of the sea defense system is further strengthened by the lines of wave defense caissons 10a which extend radially inwardly, like the spokes of a wheel, toward the centers of curvature of the curved main line of outer wave defense caissons 10.
In accordance with the invention, the particular number of wave defense and anchor tower caissons, and the arrangement of the caissons, will depend on the desired size of the area to be protected, the depth of the water at the selected site, the scale and direction of the maximum wind and wave forces generated at the selected site, and other factors. For example, one or more anchor tower caissons 12 may be interposed along the main line of wave defense caissons 10 in addition to the two corner anchor tower caissons. The leeward side of the protected area A may, if desired, be closed with a line of wave defense caissons 10 to completely enclose the protected area A. A sea lock may also be provided, either in one of the caissons or between two adjoining caissons, to permit vessels to enter and exit the protected area A. By way of example, the area A protected by the sea defense system may be made as small as, for example, 20 acres or as large as up to 1000 acres or more.
FIG. 2 shows another embodiment of integrated sea defense system installed in the ocean and in which a plurality of multi-purpose caissons 15 are provided on the leeward side of the line of outer wave defense caissons 10 in the protected area A. In this embodiment, the multi-purpose caissons 15 are arranged in a closed ring or loop configuration with the line of wave defense caissons 10 to form an enclosed area B. In this arrangement, two of the multi-purpose caissons 15 are connected to the leeward sides of two wave defense caissons 10, and the caissons 15 are interconnected to one another to completely enclose the area B.
The enclosed area B may remain filled with water to form a wet polder. One of the multi-purpose caissons 15a may be provided with a sea lock 16 for permitting vessels to enter and leave the enclosed area B. In the case of a wet polder, the body of water in the enclosed area B is completely surrounded by caissons and, from an environmental standpoint, this presents an ideal area for transferring bulk materials between vessels and the multi-purpose caissons 15 which, in that case, would be used as storage caissons. In the event of a spill or other unwanted discharge, the discharged material will be confined to the body of water within the enclosed area B, thereby enabling economic and thorough cleanup of the discharged material. The wet polder thus functions as a secure spill containment area.
Alternatively, the water within the enclosed area B may be removed and replaced by a desired level of dry fill material to form a dry polder. The fill material may be dredged from the ocean floor or may be manufactured materials. In the event the fill materials are subject to leaching wastes into the ocean, the inner walls of the caissons and the floor of the dry polder can be lined with impervious linings to prevent leaching, thus creating an environmentally secure dry material containment area.
The multi-purpose caissons 15 function to further strengthen the integrity of the sea defense system. As shown in FIG. 2, the multi-purpose caissons 15 extend in end-to-end relation transversely of the line of outer wave defense caissons 10 and are preferably arranged in lines that extend radially inwardly, like the secondary lines of wave defense caissons 10a, toward the centers of curvature of the curved main line of outer wave defense caissons 10.
The multi-purpose caissons 15, being on the leeward side of the line of wave defense caissons 10, need not be as seaworthy as the caissons 10. The multi-purpose caissons may be equipped with the necessary piping, access openings and the like to permit the transfer of bulk materials into and out of the caissons to enable the multi-purpose caissons 15 to be used as storage caissons, or to be used for manufacturing, processing or other activities.
Another embodiment of integrated sea defense system constructed of ballastable, modular caissons installed in the ocean is shown in FIG. 3. In this embodiment, a marine storage platform 20 and a marine power plant 21 are anchored or otherwise secured in the protected area A of the manmade island. A line of wave defense caissons 10c, in this case three, are provided at the leeward side of the protected area A to provide a sheltered area for a tanker or other vessel 23. By way of example, the vessel 23 may be an LNG tanker for delivering liquified natural gas to the storage platform 20 for use by the power plant platform 21 in generating electric power. A loading jetty 24 is provided adjacent the docking area, and suitable conduits, pumps and the like are provided for transporting the liquified natural gas to the various facilities. The sea defense system can likewise be used to generate electric power using liquified petroleum gas or bunker "C" or diesel oil, etc. The sea defense system may also be used to process other materials, such as petroleum products, petrochemicals and other chemicals, waste materials, etc., or as a storage complex, or for other uses.
FIG. 4 shows the general configuration of the ballastable, modular wave defense caissons 10 and multi-purpose caissons 15. The ballastable wave defense caissons 10 are preferably all of similar shape and construction. Each caisson 10 has a tapered cross section that tapers outwardly in a direction from the top to the bottom of the caisson. The bottom of the caisson 10 is provided with an annular skirt 11 which, as described hereinafter, helps secure the caisson bottom to the ocean floor by suction. The wave defense caissons 10 are preferably comprised of reinforced concrete. The caissons 10 are constructed onshore as ballastable modules and, to help render the modular caissons sufficiently buoyant to be floated to the desired ocean site and then ballasted down to the ocean floor, ballast chambers are preferably formed internally within the caissons. To provide additional ballasting capability and/or buoyancy, external detachable buoyancy enhancement devices can be used.
The ballastable multi-purpose caissons 15 preferably have a rectangular cross section to simplify their manufacture and maximize their utility for multi-purpose uses. The multi-purpose caissons need not be as rugged as the wave defense caissons 10 and thus can be manufactured more easily and at lesser expense. To enable connection of the multi-purpose caissons 15 to the sloped lee sides of the wave defense caissons 10, an interface caisson 25 or the like is provided, the interface caisson being configured to mate on one side with the sloped lee side of the wave defense caisson 10 and on the other side with the end of the multi-purpose caisson 15 or, alternatively, with the end of a transverse support caisson (which is described later). By such a construction, wind and wave forces exerted on the seaward side of the outer wave defense caisson 10, which would tend to turn the caisson, will wedge the interface caisson 25 more tightly between the wave defense and multi-purpose caissons thereby increasing the resistance to turning of the wave defense caisson 10. The use of an interface caisson 25 is limited to those configurations where this caisson can be lifted and set in place by a floating crane. For situations where this is not possible, another solution has been devised, which is the use of an outer wave defense caisson having a vertical leeward face, as shown in FIG. 8d and described hereinafter. The multi-purpose caissons 15 are preferably comprised of reinforced concrete, constructed onshore as ballastable modules, and floated to the desired ocean site.
FIG. 5 shows an example of a ballastable, modular anchor tower caisson 12 connected to two wave defense caissons 10. The anchor tower caisson 12 preferably has a polygonal cross-section and, like the wave defense caissons 10, is preferably comprised of reinforced concrete. As shown in FIG. 5, the anchor tower caisson 12 has an annular skirt 13 which defines a recessed bottom portion of the caisson. The anchor tower caisson 12 preferably has a greater height than that of the wave defense caissons 10, especially when deployed in deep open bodies of water, and extends into the ocean floor a much greater depth than the wave defense caissons.
A description will now be given, with reference to FIGS. 6 and 7, of the method of manufacturing and assembling the illustrative sea defense systems shown in FIGS. 1-3. After selection of the desired ocean site, construction of the wave defense caissons and anchor tower caissons is carried out, to the maximum extent possible, in shipyard-type facilities onshore. The relative dimensions of the wave defense caissons are determined based on various factors, as described in more detail hereinafter, including the topography of the ocean floor in the vicinity of the selected site and the maximum force winds and waves that may be encountered at the site under "worst case" storm conditions. After determination of a set of maximum wave and wind forces, the maximum lifting and turning moment forces are calculated for the wave defense caissons. Then, after the addition of an appropriate safety factor, these forces, in turn, are used to determine the mass and the precise cross-sectional design of the wave defense caissons for the selected ocean site.
After onshore construction of the wave defense caissons and anchor tower caissons, the caissons are made sufficiently buoyant to float in the ocean to the selected site. This may be done by filling ballast chambers formed in the caissons with air and/or attaching buoyancy tanks to the caissons. Should this not provide sufficient buoyancy to float the caisson, additional buoyancy can be obtained by attaching additional external buoyancy enhancement devices, such as flotation "collars" and the like. The caissons 10 are then floated to the selected site, for example, by being towed by a tugboat or other vessel.
As shown in FIG. 6, the ocean floor at the selected ocean site is suitably prepared to receive the caissons. For this purpose, a channel is dredged in the ocean floor to a depth at least as deep as the height of the caisson skirt 11. The sides of the channel are graded outwardly, in a direction away from the channel, so that the ocean floor gradually slopes upwardly on either side of the channel. The ocean floor is preferably graded to a vertical extent equal to or slightly greater than the height of the caisson skirt 11. In order to maintain the integrity of the ocean floor and to assist in distributing the weight of the caisson and the subsequently deposited material and/or armoring, one or more mats 28 may be laid over the graded areas. As shown, the mats 28, in this example, overlie the marginal edge portions of the channel to an extent coterminous with the caisson skirt 11.
After preparation of the ocean floor, the wave defense caisson 10 is floated into position over the dredged channel and then trimmed and ballasted down and sunk into place. This condition is shown in FIG. 6. The sinking of the caisson is accomplished by filling the ballast chambers 27 (only one of which is shown) in the caisson 10 with water and progressively removing the buoyancy tanks 26 and any other external buoyancy enhancement devices so that the caisson gradually descends to the ocean floor. To precisely trim the caisson 10 as it descends, a plurality of separate ballast chambers are preferably formed in the caisson at prescribed locations, and the flow of water into and out of the ballast chambers is individually controlled to effect precision trimming. After the caisson 10 is properly positioned in the dredged channel, any remaining buoyancy tanks 26 or other buoyancy enhancement devices are removed so that the caisson, due to its weight, settles onto the ocean floor. A material 29 is thereafter deposited on and around the sloped sides of the caisson 10, as shown in FIG. 7. Then a protective armoring 30 of varying size riprap and concrete blocks is deposited over both the material 29 as well as over the exposed side surfaces of the sunken caisson 10. The added material 29 may comprise sand and gravel dredged from the ocean floor or may comprise rocks or even manmade structures such as concrete. Preferably, the added material 29 comprises a first layer of material dredged from the ocean floor covered by overlying layers of rock and, finally, concrete blocks, etc.
The combined weight of the caisson 10, added material 29 and armoring 30 causes the caisson 10 to sink a certain depth into the ocean floor. The downward pressure exerted by the bottom of the caisson 10 on the ocean floor causes mud silt from the ocean floor, which is the most likely condition to be encountered, to fill the void formed by the skirt 11. Stated otherwise, as the caisson 10 settles on the ocean floor, the seawater within the recessed bottom 11a of the caisson is displaced by mud silt from the ocean floor. The filling of the void with mud silt enables a suction to be created to further secure the caisson 10 to the ocean floor. Thus if a lifting force or turning moment is applied to the caisson 10, the tendency of the caisson to lift or turn will, in part, be counteracted by the creation of a suction force at the recessed bottom 11a of the caisson.
The wave defense caisson 10 is designed such that the combined weight of the caisson, added material 29 and armoring 30 is sufficient to offset lifting forces tending to lift the caisson, turning moments tending to turn the caisson and slamming forces tending to shift the caisson which are created by maximum storm winds and waves for which the sea defense system has been designed to withstand at the selected ocean site. By such a design and construction, the caisson 10 is firmly secured in place on the ocean floor. Additional securement is provided by the suction created due to the mud silt filling the voids at the recessed bottoms of the caissons.
In the construction of a sea defense system, the wave defense caissons 10 are constructed, to the maximum extent possible, in shipyard-type facilities onshore and floated to the selected site, trimmed, and successively ballasted down to the ocean floor. After one caisson is properly positioned in place, the next-in-line caisson is ballasted down into position and connected to the previous one. Alternatively, connection can take place while caissons are still in a trimmable condition and before final settlement. Any suitable connection may be employed, and the facing ends of adjoining caissons are provided with connectors (not shown) to facilitate the connection. These connectors may be of one or more types, the simplest being cables and winches and the most complex involving interlocking connectors.
Before the main line of outer wave defense caissons 10 is secured in place, the first anchor tower caisson 12 is floated into position and ballasted down and set in place on the ocean floor. The endmost wave defense caisson 10 is then connected to the anchor tower caisson 12, as shown in FIGS. 1-3. The anchor tower caissons 12, like the wave defense caissons 10, are constructed onshore to the maximum extent possible and floated to the selected site. The anchor tower caissons 12 are also provided with recessed bottoms for creating suction forces to assist in anchoring the caissons to the ocean floor. In the case of the anchor tower caissons 12, the ocean floor preparation requires the dredging of a much deeper channel as these caissons extend to a significantly deeper depth than the wave defense caissons 10 and are firmly embedded in the ocean floor (see description of penetration factor with reference to FIG. 16).
After construction of the main line of wave defense caissons 10 and corner anchor tower caissons 12, other ballastable, modular caissons can be assembled, as needed, to obtain the desired integrated sea defense system. In the case of the FIG. 1 embodiment, this includes the construction and assembly of the secondary line of wave defense caissons 10a, 10b and the anchor tower caissons 12a. In the case of the FIG. 2 embodiment, this includes the construction and assembly of the multi-purpose caissons 15 and, if desired, construction of a dry polder in the enclosed area B. In the case of the FIG. 3 embodiment, this includes the construction and assembly of the wave defense caissons 10c.
In accordance with the invention, the sea defense system is constructed of ballastable caisson modules which can be easily de-mounted and removed from the ocean site so as to restore the site to its pre-construction state. To effect de-mounting of the sea defense system, the caissons are disconnected from one another so that each may be separately removed. In order to dislodge the wave defense caissons 10 and the anchor tower caissons 12 from the ocean floor, compressed air is injected into the recessed bottoms of the caissons through conduits (not shown) to break the suction. The seawater is pumped out of the ballast chambers formed in the caissons, and air is pumped into the chambers to increase the buoyancy of the caissons. Additional buoyancy tanks or the like are secured, as needed, to the caissons to impart sufficient buoyancy to float the caissons to the surface where they can be towed away, either for re-use at another site or for destruction. The added material and armoring can then be either removed or spread more evenly along the ocean floor so as to create fishing reefs. In this manner, the sea defense system can be de-mounted and removed at low cost and without leaving any significant permanent environmental change.
In accordance with the invention, a wave defense system can be constructed in the open ocean at sites in water depths up to 150 feet. In theory, the wave defense system could be constructed for use at even deeper depths, though it is estimated that the size and cost of the caissons would make construction impractical at depths beyond 150 feet. The wave defense system is particularly suited for use at mean-low-water depths in the range of 20 to 80 feet, with 80 feet being currently the accepted maximum mean-low-water channel depth for any commercial operations. The wave defense system is particularly suited for use at site locations in large, open bodies of water, such as along coastlines or offshore in the ocean, as well as site locations in shallower, more protected waters, such as bays, estuaries, rivers and lakes.
Detailed Description of Modular Caisson System
In accordance with the present invention, a system of standardized, ballastable, trimmable modular caissons is provided for constructing universal, manmade wave defense systems for use over a wide range of site conditions in bodies of water of various types and depths and subjected to any kind of storm or tsunami. The modular system comprises different types of primary modular caissons of standardized shapes and proportions, wherein each different type of caisson module is designed to perform one or more specific functions in the overall wave defense system. The caisson modules can be suitably scaled to size and assembled in different combinations to construct a multitude of differently configured wave defense systems.
The individual caisson modules can be manufactured, to the maximum extent possible, under cost-controlled conditions in shipyards or shipyard-type facilities onshore and then towed to, and assembled at, the site where the wave defense system is required. The caisson modules are capable of being scaled and assembled in different combinations, so that the overall scale and modular assembly of the wave defense system is capable of withstanding and overcoming the maximum hydrodynamic and wind forces that can be generated at a preselected site, with no larger modules, nor greater number of modules, nor greater degree of modular assembly, being utilized than are absolutely necessary for that particular site.
The wave defense system is designed so that no wave over-topping occurs, so that the area on the lee side of the system is fully protected to form a manmade or artificial island to provide secure maneuvering, docking and anchoring areas for all types of vessels, even when the site is subjected to maximum wind and wave attack.
Due to the modular nature of the wave defense system, the caisson modules can be readily removed, if desired, at the end of the useful life of the wave defense system, thereby returning the site as closely as possible to its pre-construction state. This is an important consideration in this era of increasing environmental awareness and regulation.
In accordance with one aspect of the invention, the modular caisson system consists of a plurality of different types of primary, ballastable, trimmable caissons which may be assembled in combinations of two or more types to construct different manmade wave defense systems. In the preferred embodiment, there are five fundamental types of primary, standardized, ballastable modular caissons which constitute the basic building blocks of all the wave defense systems. The five primary, ballastable caissons are shown to scale relative to one another in FIG. 8. The five primary modular caissons comprise anchor tower caissons, outer wave defense caissons, transverse support caissons, inner wave defense caissons and multi-purpose caissons. One or more of the types of primary caissons, or all five, can be combined to form integrated wave defense systems, various examples of which are shown in FIGS. 1-3 and 10-13.
FIG. 8a shows a side elevation of an anchor tower caisson 40 embedded on the ocean floor. The anchor tower caisson 40 preferably has a polygonal cross section and has an annular skirt 41 which defines a recessed bottom portion of the caisson to aid in securing the caisson bottom to the ocean floor by suction. The anchor tower caisson 40 is similar to the previously described anchor tower caissons 12. A modified form of anchor tower caisson 45 is shown in FIG. 8b, and such comprises a truncated version of the anchor tower caisson 40.
For purposes of illustration, all of the primary caissions described herein are shown as having recessed bottom portions. In certain circumstances, however, such as when the floor of the dredged trench (in which the caissons are sunk) is of a hard material, such as a hard clay, the recesses in the bottom portions may be dispensed with. This is because in hard material the recessed bottoms of the caissons loose their ability to act as "suction cups", which is their function in soft material such as a silt or silt/clay. The decision as to whether to use caissons with or without recessed bottom portions depends on whether or not the outside peripheral edges of the recessed bottoms are capable of aiding the caisson bottoms to penetrate into the hard floor of the trench, which depends primarily on the soil mechanics of the particular site in question. Further, it should be noted that when conditions beneath the floor or bed are extremely fluid, it may be necessary to drive piling clusters deeply into the bed, or use other well-established methods, to further support the anchor tower and other caissons.
There are several main purposes of the anchor tower caissons 40. One is to anchor the ends, or one end, of the wave defense system by providing a substantial mass firmly embedded in the seabed, lake bed, river bed, etc. to assist in maintaining the integrity of the wave defense system between the ends thereof or between one end thereof and the shore. Another purpose is to provide a high and readily identifiable radar target for vessels approaching the wave defense system, thus providing an important navigational aid to ships and planes in the neighborhood of the system. Another purpose is to provide a high location overlooking the wave defense system to house a command and control center for excercising vessel traffic control, fire control, security control, air-sea rescue control, disaster control, etc. In addition, the top decks of the relatively high anchor tower caissons 40 are ideal locations for helicopter landing pads to allow for optional use of helicopters to transport personnel, supplies, etc. and to assist in carrying out the various control functions.
To enable the anchor tower caissons 40 to perform these functions, the caissons must rise a major distance above the height of the other modular caissons of the wave defense system. Further, due to the height of the caissons 40, they provide optimal locations for garaging and maintaining all of the mobile wheeled vehicles used at the installation, while providing ample space for administrative offices, first aid facilities, dormitories, cafeterias, stores, etc.
By comparison, there is no reason for the truncated anchor tower caissons 45 to rise above the height of the other modular caissons of the wave defense system. The main function of the truncated anchor tower caissons 45 is to provide additional support to sections of the wave defense system at points between the end anchor tower caissons, especially where the length of any section is unusually long and therefore may require added support. The truncated anchor tower caissons 45 are typically interspersed along a line of wave defense caissons and ideally should be at the same height as the wave defense caissons to facilitate provision of a service road running the length of the wave defense system. In such a case, the top decks of the truncated anchor tower caissons 45 can be used as parking areas for vehicles, such as during emergency situations and the like.
Another use for the truncated anchor tower caissons 45 is as a base for supporting a lighthouse which would function as an alternative aid to navigation. FIG. 81 shows a lighthouse 46 constructed atop the truncated anchor tower caisson 45, and FIG. 8m shows a lighthouse 46a constructed atop a slightly modified truncated anchor tower caisson 45a having, for technical and aesthetic reasons, a sloped upper section 48 which slopes inwardly in the upward direction so that the anchor tower caisson and lighthouse merge together more gradually and gracefully than in the case of FIG. 81. The provision of a lighthouse is particularly suited for aesthetic and visual impact reasons in the case of wave defense systems used for coastal protection and placed within sight of shore.
In some instances, the height of the truncated anchor tower caissons 45 may be less than that of the line of wave defense caissons. For example, in a wave defense system requiring sluice gates, the sluice gates would be incorporated in the truncated anchor tower caissons which, in that case, would have a height below that of the wave defense caissons so that the height of the sluice gates, when fully raised, is approximately the same as the height of the adjoining wave defense caissons. In other words, the top deck of the truncated anchor tower caissons would be located below the level of the top of the line of wave defense caissons.
FIGS. 8c and 8d show side elevations of two different outer wave defense caissons 50 and 55. Each of the caissons 50 and 55 is provided with an annular skirt 51 to assist in securing and holding the caissons to the ocean floor by suction. The outer wave defense caisson 50 is designed for use at sites subjected to minimum "worst case" hydrodynamic conditions at minimum commerical depths, whereas the outer wave defense caisson 55 is designed for use at sites subjected to maximum "worst case" hydrodynamic conditions at maximum commercial depths. The outer wave defense caisson 50 is similar to the previously described wave defense caissons 10 and has a tapered cross section that tapers outwardly in the downward direction on both the windward and leeward sides 52 and 53 of the caisson. In this design, the slope of the windward side 52 is the same as that of the leeward side 53, and the two sides slope outwardly for a major part of their downward extent.
The outer wave defense caisson 55 is designed somewhat differently than that of the outer wave defense caisson 50 and has its center of gravity shifted in the leeward direction as compared to that of the caisson 50. The windward side of the caisson 55 has a split slope having an upper sloped portion 56a having a relatively gradual rise and a lower sloped portion 56b having a relatively steep rise. The caisson 55 is designed so that most or all of the upper sloped portion 56a extends above the water surface (at mean low water) and most or all of the lower sloped portion 56b lies below the water surface. The leeward side of the caisson 55 has a sloped top portion 57 and a generally horizontal ledge porton 58, both of which are disposed entirely above the water surface, and a vertical portion 59 which is provided to accommodate placement of transverse support caissons, as described below. As shown in FIG. 8d, the upper part of the outer wave defense caisson 55 has a tapered cross section that tapers outwardly in the downward direction on both the windward and leeward sides in the region of the opposed sloped portions 56a and 57.
While the two forms of wave defense caissons 50 and 55 are both designed for use as outer wave defense caissons, the caisson 50 is designed for use at locations subjected to minimum "worst case" wave and wind conditions whereas the caisson 55 is designed for use at locations, generally in deeper waters, subjected to maximum "worst case" wave and wind conditions. This will be explained in more detail with reference to FIGS. 8h-8k.
Outer wave defense caissons for use in large, open bodies of water must be designed to withstand maximum scale wind and wave attack, such as that of a maximum scale hurricane, typhoon, cyclone or tsunami. Maximum scale waves tend to slam and lift any caisson they encounter because the buoyancy of the caisson is increased as the wave impinges on the caisson. When the wind forces pressing against the windward face of the caisson are added to the slamming and lifting forces created by the waves, turning moment forces are generated which, when combined with the tendency of the caisson to be lifted by the waves, can result in the caisson being raised from its position on the seabed, lake bed, etc. and turned over (toppled) and swept away (see description of toppling factor with reference to FIG. 15). Under such conditions, the integrity of the wave defense system can be broken, leading to widespread destruction on the leeward side.
A wave defense caisson having vertical windward and leeward faces will be subjected to greater relative lifting and slamming forces, and have a greater potential turning moment, than will a caisson of similar width but with sloping windward and leeward faces. For these reasons, the outer wave defense caisson 50 shown in FIG. 8h was designed with sloping rather than vertical faces. The caisson 50 has the preferred cross section for outer wave defense caissons for use in the open ocean for a wide range of hydrodynamic and site conditions. It has been found, however, that the cross section of the caisson 50 is not optimal for meeting the engineering design requirements under the most severe hydrodynamic and site conditions such as might occur in large, open bodies of water up to a maximum commercial depth. Under maximum hydrodynamic and site conditions, the outer wave defense caisson 50 would have to be so large as to be unfeasible from a technical and economic standpoint.
A comparison of FIGS. 8h and 8i illustrates this point. In these figures, the outer wave defense caissons 50 and 55 are drawn to the same relative scale for use at a site subjected to maximum hydrodynamic and site conditions at a maximum commercial depth. The caisson 50 is designed to substantially prevent wave over-topping, whereas the caisson 55 is designed to permit over-topping of waves which are then absorbed by an inner wave defense system (described hereinafter). In this typical example, the over-topping design of the caisson 55 has a width w approximately 60% that of the non-over-topping design of the caisson 50 and a height h approximately 70% that of the non-over-topping design, thus making the wave over-topping caisson 55 significantly more feasible to construct from a technical and economic standpoint.
Furthermore, the over-topping design of the outer wave defense caisson 55 offers other significant advantages over the non-over-topping design of the caisson 50, especially when the caissons are used under maximum hydrodynamic and site conditions and at a maximum commercial depth. These advantages include the following:
(1) The gradual slope of the main windward face 56a of the wave over-topping caisson 55 reduces the forces to be absorbed by the caisson in the face of maximum wave attack. A relatively greater proportion of these wave forces is transferred up the windward face of the caisson and over the top thereof than is the case in the wave non-over-topping caisson 50 whose main windward face 52 has a much steeper slope.
(2) The wave forces that must be absorbed by the wave over-topping caisson 55 are transferred more directly into a downward, vertical component than is the case with the wave non-over-topping caisson 50. This lessens the tendency for the caisson 55 to be lifted up and over-turned as compared to the caisson 50. When under wave attack, the wave over-topping caisson 55 experiences a significantly less increase in buoyancy as compared to that of the wave non-over-topping caisson 50.
(3) The more gradual slope of the windward face 56a of the wave over-topping caisson 55 reduces the slamming effect of maximum strength waves on the caisson when compared to the wave non-over-topping caisson 50 with its steeper windward slope 52.
(4) The optimal engineering design of the windward slope of the wave over-topping caisson 55 has two individual sloped portions 56a, 56b. The lower sloped portion 56b is at a much steeper angle relative to the upper sloped portion 56a. This allows for a greater volume and, therefore, a greater weight, of riprap to be placed on and against the windward face 56 of the wave over-topping caisson 55 as compared with the wave non-over-topping caisson 50 which has a windward face 52 of constant slope. This is illustrated in FIGS. 8j and 8k. In the case of the wave over-topping caisson 55 shown in FIG. 8k, the split-slope configuration allows approximately one-third more volume (and more weight) of riprap 30 to be placed thereon as compared to the non-split-slope configuration of an otherwise similar caisson 55x shown in FIG. 8j. The added weight of riprap 30 borne by the wave over-topping caisson 55 counteracts the lifting and turning forces.
(5) As shown in FIG. 8i, the leeward face 59 of the wave over-topping caisson 55 is perpendicular to the bed from at least the mean-low-water level to the bottom of the caisson. This allows for the juxtapositioning of a transverse support caisson (as explained hereinafter) where hydrodynamic and site conditions so dictate, whereas such is not possible in the case of the wave non-over-topping caisson 50. The provision of a transverse support caisson not only eliminates any tendency of the outer wave defense caisson 55 to shift laterally, due to the slamming action of the waves, but also adds to those countervailing forces that oppose the tendency of the caisson to be overturned.
FIG. 8e is a side elevation of a transverse support caisson 60. The caisson 60 preferably has a rectangular cross section and an annular skirt 61 to assist in holding the caisson in place by suction on the ocean floor. The caisson 60 has a vertical windward side 62 and a vertical leeward side 63 and is provided with a plurality of transverse ports 64 for permitting water to flow laterally through the caisson to dissipate wave energy and balance hydrodynamic forces on either side of the caisson. For ease of illustration, the transverse ports 64 have been shown in FIG. 8e as being rounded in shape although as site requirements dictate, they may have other shapes.
FIG. 8f shows a side elevation of an inner wave defense caisson 70. The caisson 70 has an annular skirt 71 at the bottom thereof to assist in holding the caisson on the ocean floor by suction. The windward side of the caisson 70 has a lower vertical wall portion 72 which extends from the ocean floor to above the water surface, a sloped portion 73 and an upper vertical wall portion 74. The leeward side 76 of the caisson 70 extends vertically from the top to the bottom of the caisson.
FIG. 8g shows a side elevation of a multi-purpose caisson 80. The caisson 80 has an annular skirt 81 to help hold the caisson on the ocean floor by suction. The multi-purpose caisson 80 may, for example, be similar to the storage caissons 15 and preferably has a rectangular cross section to simplify its design and construction and minimize its cost of manufacture; while at the same time, maximizing the internal volume of the multi-purpose caisson so that it may be used more effectively for the storage of materials, processing of materials, institutional purposes, administrative purposes, residential purposes and the like as described more specifically hereinafter.
Further it should be noted that the leeward face of the caissons 70 most usually would be the same height as the windward face of the caissons 80 against which they are to be placed in juxtaposition in any single integrated wave defense system.
The five primary, ballastable, trimmable caisson modules can be combined in various arrangements to construct universal, environmentally safe, wave defense systems. In a typical installation, a line of outer wave defense caissons 50 or 55 is anchored at one or both ends of the line by an anchor tower caisson 40 or 45. One or more anchor tower caissons may also be placed at intermediate points along the line of outer wave defense caissons. One or more lines of inner wave defense caissons 70 and/or multi-purpose caissons 80, as required by the hydrodynamic and underlying conditions at the selected site, are provided in juxaposition with, and on the leeward side of, the line of outer wave defense caissons. One or more transverse support caissons 60, as required by the hydrodynamic and underlying site conditions, are placed between and transverse to the lines of outer and inner wave defense caissons. The transverse support caissons together with the line or lines of inner wave defense and/or multi-purpose caissons constitute a reinforcement sub-system for the overall wave defense system. The reinforcement subsystem reinforces the line of outer wave defense caissons and prevents them from being lifted, slammed or overturned by maximum force winds and waves that may be generated at the site in question.
By way of illustration, FIG. 9 is an explanatory diagram, partly in cross section, of a typical, integrated wave defense system constructed using the modular caisson system of the invention and designed specifically for use at a location involving maximum adverse site conditions, maximum depth, and exposure to maximum hydrodynamic wave and wind conditions, such as those that can be generated by a maximum scale hurricane, typhoon or tsunami. The wave defense system comprises a line of outer wave defense caissons 55 anchored at opposite ends by anchor tower caissons 40 (only one of which is visible in the figure). As shown, the base of the anchor tower caisson 40 is embedded much deeper in the ocean floor than the other caissons. A line of inner wave defense caissons 70 extends in juxtaposition with the line of outer wave defense caissons 55 on the leeward side thereof. A line of multi-purpose caissons 80 extends along the line of inner wave defense caissons 70 on the leeward side thereof. A plurality of transverse support caissons 60 (only one of which is visible) are interposed between the lines of outer and inner wave defense caissons 55 and 70 and extend lengthwise in the transverse direction relative to the lines of outer and inner wave defense caissons. The vertical windward sides 62 of the transverse support caissons 60 confront the vertical leeward side portions 59 of the outer wave defense caissons 55, and the vertical leeward sides 63 of the caissons 60 confront the vertical windward wall portions 72 of the inner wave defense caissons 70. The vertical leeward sides 76 of the inner wave defense caissons 70 confront the vertical windward sides of the multi-purpose caissons 80.
Though not shown, means are provided for interconnecting adjoining caissons in the lines of caissons. Any suitable connection may be employed, and preferably the facing ends of adjoining caissons are provided with connectors such as interlocking connectors or other suitable means to enable connection and disconnection of adjoining caissons. Also not shown are the shock absorbing means, such as fenders, bumpers and the like, which are interposed between adjoining caissons to absorb and distribute impact forces between the caissons, and, where necessary, to prevent the passage of water between the caissons.
In designing the integrated wave defense system shown in FIG. 9, the modular caissons are selected and scaled to be no larger than necessary for the particular site. Only the minimum number and type of modular caissons are used, and the wave defense system is designed to withstand and overcome the maximum wind and wave forces that can be generated at that site. The method of constructing the wave defense system is the same as that described above with reference to FIGS. 6 and 7. All of the modular caissons are designed to be ballastable and trimmable and, to the maximum extent possible, to be manufactured in shipyard-type facilities onshore.
Maximum economic advantage is gained where the caissons can be manufactured as monolithic modules in shipyard-type facilities onshore. However, in cases where draft or other constraints prevent such monolithic manufacture, all modular caissons can be manufactured in sections by assembly of manufactured sub-assemblies or by further construction, and/or assembly of sub-assemblies, on top of a caisson base section where such further construction, and/or assembly of sub-assemblies, is undertaken at a location where adequate drafts are available and where the base elements sections act as construction "platforms" for further construction and/or assembly of sub-assemblies. For maximum economic advantage, such base sections would be manufactured at a shipyard-type facility onshore up to the maximum draft available at that facility and in the navigation channel leading from that facility to open water.
To undertake this in the most cost-effective manner, manufacturing should, to the maximum extent possible, result in components that can be floated and towed by tugs to installation assembly sites and, only when this is not feasible, should components be designed to be transported to installation sites by heavy lift vessels and/or crane ships. The objective in both instances is to maximize construction under cost-controlled conditions in shipyards or shipyard-type facilities onshore, and minimize construction offshore.
To meet this objective requires that each caisson be designed so that its construction can be broken down into discrete sections. For example, caisson bottom sections (which can act as construction platforms) and lengths of side walls and end walls, can be designed and constructed as discrete sub-assemblies. The sub-assemblies preferably have a double-wall design with internal ballast tanks therebetween, which enables the sub-assemblies to be floated and towed to installation sites.
The buoyancy required for such operations can be supplied by filling the internal ballast tanks with air and/or by attaching one or more temporary, external buoyancy enhancement devices, such as flotation "collars" or the like. Alternatively, modified-type heavy lift vessels can cradle a sub-assembly, and use of these vessels, with their greater surplus buoyancy, in effect, transfer some of the weight of the sub-assembly to themselves. For those components that cannot be floated, even with the assistance of external buoyancy enhancement devices, they should be designed and constructed so that, to the maximum extent possible, they can be carried by barges or vessels including crane ships for installation at the site.
Once manufactured, all modular caissons and/or their platforms and/or sub-assemblies are designed to be floated to the installation site, for example, by towing the caissons by a tugboat or other vessel or by placing sub-assembly parts on heavy lift vessels, crane ships, etc. At the selected site, a trench is dug by dredging, and the floor of the trench is prepared to receive the modular caissons. This may include mats 28, depending on the nature of the floor in the trench. The decision where and if to use such mats (in order to maintain the integrity of the seabed, lake bed, river bed, etc. and to assist in distributing the weight of the armor, etc.) is dependent on the soil mechanics at the site in question. For example, mats are more likely to be employed under armor, etc. where bed conditions include silts, etc. and are generally not needed where bed conditions include hard clays, etc. The modular caissons are floated into position, trimmed, and then ballasted down and sunk into place on the bed. An armor apron 30 of varying size rock, concrete block and riprap is placed, as needed, on and against the sides of the modular caissons to provide for a first line of wave energy absorption, add necessary mass to the overall wave defense system, and eliminate scouring around the wave defense system. Depending on the severity of the hydrodynamic conditions at the site in question, additional armor aprons 30a and 30b may be needed.
The integrated wave defense system is constructed such that at the end of the useful life thereof, the modular caissons can all be disassembled, where necessary, ballasted up and towed away, either for reuse at another site or for destruction, thereby leaving the site as nearly as possible in its pre-construction state. Any residual underwater mounds of rock or concrete armor can be re-shaped to provide fishing reefs. The wave defense system can thus be de-mounted and removed at relatively low cost and without leaving any significant permanent environmental change.
FIG. 9 illustrates an inner wave defense and reinforcement sub-system for reinforcing the line of outer wave defense caissons 55. The sub-system comprises the transverse support caissons 60, the line of inner wave defense caissons 70 and the line of multi-purpose caissons 80. The reinforcement sub-system reinforces and supports the line of outer wave defense caissons 55 and prevents them from being lifted, slammed or overturned by maximum force wind and waves. Depending on the maximum adverse site conditions, it may be necessary to place a transverse support caisson 60 behind each one of the outer wave defense caissons 55, though that number of transverse support caissons would not normally be required, especially if the line of outer wave defense caissons 55 is curved or angled outwardly in the direction of the prevailing winds and waves. For example, if the outer wave defense caissons are deployed in a straight line, as might be the case in coastal protection systems, a transverse support caisson would likely be placed behind each outer wave defense caisson or, if not, some other caisson interlocking mechanism would have to be employed. On the other hand, if the outer wave defense caissons are deployed in a curved line, especially in an arch configuration, transverse support caissons may not be needed behind each outer wave defense caisson and placement behind intermediate ones may suffice.
Under the maximum adverse site conditions, maximum water depth and maximum hydrodynamic wave and wind conditions considered for the wave defense system shown in FIG. 9, a major problem is created due to the energy potential of waves over-topping the line of outer wave defense caissons 55. If the line of outer sea defense caissons 55 is built to entirely eliminate the possibility of wave over-topping, the resulting structure would be so massive as to be impractical from engineering and cost standpoints. In accordance with the present invention, this problem has been solved by designing the line of outer wave defense caissons 55 to accept a significant amount of wave over-topping and by providing a uniquely designed wave over-topping absorption, containment and dispersion subsystem within the reinforcement sub-system. Such a subsystem must be designed as an integral part of the reinforcement sub-system which, in turn, must be designed as an integral part of the overall wave defense system.
The wave over-topping absorption, containment and dispersion sub-system comprises two of the five primary modular caissons, namely, the transverse support caissons 60 and the inner wave defense caissons 70. From a structural point of view, the inner wave defense caisson 70 is almost as massive as the multi-purpose caisson 80 but differs therefrom in significant respects. Namely, the inner wave defense caisson 70 has an extensive sloping windward face 73, and perpendicular walls 72 and 74 above and below the sloping face 73. The two walls 72,74 create wave-slamming surfaces that serve to create counter waves that contribute their energy towards breaking up the incoming over-topping waves. The extensive windward facing slope 73 serves to cause any residual surge of water up the slope, known as "uprush", to lose energy and fall back, known as "downrush", onto the incoming over-topping waves.
The transverse support caissons 60 have a relatively low profile and have large transverse holes 64 extending therethrough. For ease of illustration, these holes are shown to be elliptical although other shapes may be required under other circumstances, such as where riprap 30a and/or 30b is required. These features allow for greater lateral dispersion of any build-up of water levels resulting from waves over-topping the line of outer wave defense caissons 55, and falling back as "downrush" from the line of inner wave defense caissons 70. In this manner, the inner wave defense caissons 70 and the transverse support caissons 60 jointly constitute the wave over-topping absorption, containment and dispersion subsystem, which must be included in the overall wave defense system when the hydrodynamic, wind and site conditions are such as to require a maximum scale integrated, overall wave defense system.
The scale of the modular caissons to be used at a particular site is a function of the maximum hydrodynamic and wind forces that are expected to be generated at that site. These forces are largely a function of the height and velocity of the maximum strength waves and the maximum wind pressure that are expected to be generated at that site. In theoretical terms, the energy generated by a wave is given by the equation:
E=1/8 (pgH 2 )
where E=wave energy in joules per square meter (Jm -2 )
ρ=density of water in Kgm -3
g=9.8 ms -2
H=wave height in meters
In actual practice, the height of the maximum wave, and its maximum speed, for the purposes of calculating the scale of the modular caissons can only be derived when site specific data are known.
In large bodies of water, the engineering forces generated by maximum force winds and waves can vary greatly, depending on the location of the particular site under consideration. For example:
(1) A group of waves, such as generated by a hurricane, can be more damaging to a wave defense system than a single, very high wave, such as generated by a tsunami.
(2) An irregular train of waves can be more destructive than a regular train of waves.
(3) Breaking waves can exert much greater pressures than non-breaking waves.
In addition, the extent to which wave-generated forces can vary at different locations, especially near coastlines or shorelines, is further compounded by the fact that the bottom usually slopes upward as the waves approach the coastlines or shorelines, thereby increasing bottom friction ("bottom effect") which, in turn, tends to reduce wave height. On the other hand, depending on the degree of rise of the bottom slope as it approaches the coastline or shoreline, the shoaling effect can increase wave height and may also contribute to the creation of breaking waves.
This complexity of forces that can be generated by waves, especially as they approach coastlines or shorelines, must be taken into account in the engineering layout and design of wave defense systems. In view thereof, the necessary calculations to properly scale the modular caissons requires an interactive methodology between, on the one hand, ocean engineering calculations and geophysical site studies and data, and on the other hand, the results of accurately scaled physical hydrodynamic model tests (hydraulic model tests) in properly calibrated hydrodynamic test tanks (wave basins and wave flumes) where actual site conditions can be simulated. Hydrodynamic (hydraulic) model tests are essential if the engineering design of any wave defense system is to proceed on a sound basis.
Test models are usually constructed to a linear scale of 1:100 to 1:150 (model to prototype). Models are designed and model tests operated in accordance with Froude's model laws. Models are constructed of concrete on a wave basin floor, usually inside a large hangar or shed, which protects against wind, rain, snow, etc. The wave basins have to be extremely well lighted to assure that sharp photographs can be taken of wave patterns and the like. Waves are reproduced to scale by a wave-making machine. Wave heights are typically measured by electric gauges. The impact and effects of maximum strength waves on a wave defense system will be felt (by reflected waves) over a considerable distance surrounding the system. It is essential that the impact and effects over this entire area are accurately measured. For this reason, the size of the wave basin must be many times larger than the models being tested. For example, a model of a large wave defense system might require a wave basin as large as a football field.
It is as a result of long-term evaluation of the wide range of forces that can be generated over large bodies of water, that a solution involving the use of five primary, ballastable, trimmable, modular caissons has been developed.
The overriding importance of considering site specific data and hydrodynamic tank testing in determining the proper scaling of the modular caissons cannot be overemphasized. The complexity surrounding the theoretical calculations in determining proper scaling, and the absolute essentiality of undertaking these calculations in an interactive manner together with the results from site specific hydrodynamic tank tests, can be readily appreciated from a review of the site specific variables involved. The maximum wave and wind forces at a particular site are a function of a number of variables, including:
(1) The fetch, or distance, over which maximum force winds and waves can travel unobstructed before they reach the site.
(2) The velocity of the wind blowing over this fetch.
(3) The duration over which this wind blows.
(4) The maximum depth of water at the site, taking into account maximum tide and storm surge levels.
(5) The degree of rise, or slope, of the seabed, lake bed, etc. as it approaches the site, especially from the directions of maximum wind and wave attack.
(6) The velocity and direction of the currents around the site.
(7) The extent of the scour effect around the site.
High velocity winds, blowing over a long fetch for an extended period of time, create powerful waves. As these waves approach a coast, especially if, at the same time, there is also a steep rise in the bed surrounding the site, the waves can generate enormous destructive power. An example of this power can be seen when waves of only 30 feet in height, but propelled by hurricane force winds, broke up the tanker Brea when it was wrecked on the coast of the Shetland Islands in January 1993. It is not unusual, however, for the maximum wave height around the Shetland Islands to reach twice, or more than twice, this level.
For a wave defense system to be truly universal, consideration must also be given to tsunamis and the extreme wave conditions they represent. For example, in 1992, two large-scale tsunamis came ashore on Pacific coastlines; one in Nicaragua and one in Indonesia. In both cases, these tsunamis, created by major underwater earthquake and/or volcanic events, resulted in waves reported to be over 60 feet high hitting the coasts with widespread loss of life and destruction. The wave defense system of the present invention is the only known modular caisson system in the world that can be scaled up to the size necessary to withstand full-scale tsunamis such as those experienced in the Pacific in 1992.
It is this maximum hydrodynamic condition that dictates the scaling of the modular caissons and the final engineering calculations used in the design of a wave defense system for a particular site. Failure to understand and design against maximum level forces can lead to disastrous results.
For example, it was because of miscalculation, and a misunderstanding, of both the scale and the direction of the maximum wind and wave forces that could be generated at Signes, Portugal that led to the destruction of the 100 foot deep breakwater at this site in its first Atlantic storm. In fact, it was only after Dutch ocean engineers were able to simulate the actual destruction of the Signes breakwater in a wave flume test series that proper calculations could then be started, leading to the reconstruction of the breakwater.
From the standpoint of cost, the depth of water at a selected site is important, because the cost of construction of a wave defense system using the modular caissons tends to increase as a square of the height of the maximum wave that can be generated at that site. For any implementation of the modular caisson system in large, open bodies of water to be commercially viable, the site depth should be kept to a minimum, generally no greater than the depth (at mean low water) necessary to accommodate the private sector and/or public sector uses at that site. For example, if the primary use of the wave defense system is to create a protected harbor for general cargo vessels, then the navigation depth of water required at mean low water (M.L.W.), including clearance under the keel, is currently about 45 feet. On the other hand, if the primary use is to create a harbor for maximum-size bulk carriers, then the navigation depth is currently about 80 feet (M.L.W.). Of course, a wave defense system must be designed to provide protection above this navigation depth to account for tidal change and storm surge. By contrast, a wave defense system having as its primary use coastal protection against beach erosion could be located in depths as little as 20 feet (M.L.W.) or even less depending on site conditions.
The commercial depth range for ocean-going vessels, which includes maximum tide and storm surge conditions in addition to maximum navigation depth requirements, currently lies between 20-100 feet for the vast majority of the world's ports. Technically, however, it is possible to consider constructing wave defense systems using the five primary, ballastable, modular caissons in even deeper waters, outside this commercial depth range. The construction of wave defense systems in shallower, relatively protected, waters, such as bays, estuaries, rivers, lakes and the like is discussed later. Even though the current extremes of the commecial depth range for ocean-going vessels probably differ by no more than 70-80 feet, the maximum force waves and winds that can be generated within this depth difference can vary greatly. As a result, the configuration and cost of construction of a wave defense system located in large, open bodies of water can also vary greatly within such a relatively small vertical distance.
The five primary, ballastable, standardized modules have been developed to encompass the full range of private and/or public sector uses for wave defense systems, constructed using the modular caissons, taking into account the site specific variables described previously. General engineering designs have been developed for each of three, typical, integrated wave defense systems at sites located in large, open bodies of water experiencing different site specific conditions. FIGS. 10-12 are drawn to relative scale and show the layouts of these systems.
FIG. 10 shows a wave defense system developed for a site located in a large, open body of water and experiencing minimum fetch, wind velocity, duration, tide, surge, rise, currents and scour effect at minimum commercial depth (case A). FIG. 11 shows a wave defense system developed for a site located in a large, open body of water and experiencing intermediate level fetch, wind velocity, duration, tide, surge, rise, currents and scour effect at an intermediate commecial depth (case B). FIG. 12 shows an integrated wave defense system developed for a site located in a large, open body of water and experiencing maximum fetch, wind velocity, duration, tide, surge, rise, currents and scour effect at a maximum commercial depth (case C). The modular caissons in each of the wave defense systems shown in FIGS. 10, 11 and 12 are drawn to the same relative scale. It is obvious that the increase in scale between the three wave defense systems of cases A, B and C is not a linear function; instead, it is closer to being an exponential function. A comparison of the scale of these three cases shows the construction cost "penalty" that must be paid for going into deeper waters, especially at a site that is also exposed to maximum wind and wave forces, such as would be the case where a maximum scale hurricane, etc. causes breaking waves at the site in question.
One of the major factors causing this exponential increase in scale is due to the so-called "bottom effect." In shallow waters, there is known a phenomenon that results in waves at shallower depths, such as in case A, being affected to a relatively greater extent by the "drag" or "bottom effect" exerted on the waves by the proximity of the bed (seabed, lake bed, etc.). Conversely, as the depth of water increases, the relative effect of this "drag" decreases. As a result, if all other variables are equal, and depending on where the countervailing shoaling effect occurs, the storm design wave at the deeper site, such as in case C, can be exponentially larger than the storm design wave at the shallower site (case A). This, in turn, means that the lifting, slamming and overturning forces on the outer wave defense caissons and the anchor tower caissons generated by the larger storm design wave at the deeper site can be exponentially larger than those generated by the smaller storm design wave at the shallower site. This phenomenon, together with the increased forces generated by the greater fetch, wind velocity, duration, rise, tide, storm surge and scour assumed for the deeper case C site, explain why the scale of the wave defense system in case C has to be so much greater than in case A.
The general engineering design and layout of the differently scaled wave defense systems for cases A, B and C are shown in FIGS. 10, 11 and 12. Specifically, the general engineering design and layout for the five primary, ballastable, modular caissons to form single, integrated wave defense systems in large, open bodies of water have been established for each of the three cases, and such covers the general design and layout required for any wave defense system within, as well as outside, the full range of commercial depths.
As noted earlier, in actual practice, such general engineering designs and layouts must be modified to take into account the results of site-specific geophysical studies and subsequent hydrodynamic model testing and further ocean and civil engineering calculations.
FIG. 10a is a cross-sectional side elevation of an integrated wave defense system at a site experiencing minimum conditions of fetch, wind velocity, duration, tide, surge, rise and scour effect and located at a minimum commercial depth (case A), and FIG. 10b is a top plan view of the wave defense system. In case A, it was found that a single, integrated wave defense system could be provided using only a line of outer wave defense caissons 50a and anchor tower caissons 40a at the opposite ends of the line of caissons 50a. Under this set of minimum conditions, it was found that neither a line of inner wave defense caissons nor provision of transverse support caissons were needed in order to provide the degree of wave defense required at such a site. It should be noted that a site located in large, open bodies of water that meets this set of minimum criteria, while not impossible to find, will almost certainly not be the norm.
For purposes of establishing a common scale to allow comparison between FIGS. 10, 11 and 12, an LNG bulk carrier 91 is shown in each figure. In FIG. 10, the LNG bulk carrier 91 is shown alongside a line of multi-purpose caissons 80a. Alternatively, quay/dock caissons 90 can be used in place of, or, as shown in FIGS. 11 and 12, in addition to the multi-purpose a. The quay/dock caisson 90a does not constitute one of the standardized, primary modular caissons which make up the modular caisson system of the invention, but rather is a secondary caisson for use as a quay or dock. The quay/dock caisson 90 provides no structural support in the wave defense system and may be replaced by any other suitable structure.
FIG. 11a is a cross-sectional side elevation of a wave defense system constructed of primary modular caissons at a site located in a large, open body of water experiencing intermediate fetch, wind velocity, duration, tide, surge, rise and scour effect conditions and located at an intermediate commercial depth (case B), and FIG. 11b is a top plan view of the wave defense system.
In case B, it was found that, as a result of the significant forces generated by residual waves over-topping the line of outer wave defense caissons 55b, an additional line of inner wave defense caissons had to be provided. For this purpose, a line of multi-purpose caissons 80b is provided on the leeward side of the outer wave defense caissons 55b, the outer and inner lines of wave defense caissons extending in juxtaposition to one another.
In addition, in case B, it was found that the extent of the lifting, slamming and overturning forces on the outer wave defense caissons 55b required further support. For this purpose, the transverse support caissons 60b are placed between and transversely to the lines of outer and inner wave defense caissons 55b and 80b. The transverse support caissons 60b together with the line of multi-purpose caissons 80b constitute a reinforcement subsystem which effectively reinforces the line of outer wave defense caissons 55b.
In this installation, the outer wave defense caissons 55b, transverse support caissons 60b and multi-purpose caissons 80b together with the anchor tower caissons 40b constitute and act as one integrated wave defense system under the intermediate conditions assumed for case B sites. A line of quay/dock caissons 90b extends along the leeward side of the line of multi-purpose caissons 80b, and the LNG bulk carrier 91 is shown for purposes of establishing a common scale to allow comparison between the wave defense systems for cases A, B and C.
FIG. 12a is a cross-sectional side elevation of a wave defense system using primary modular caissons designed for a site located in a large, open body of water and experiencing maximum fetch, wind velocity, duration, tide, surge, rise and scour effect and located at a maximum commercial depth (case C), and FIG. 12b is a top plan view of the sea defense system.
Case C is designed to withstand the maximum level of wind and wave forces that can be generated as well as the maximum lifting, slamming and overturning forces and levels of wave over-topping that can occur under such maximum conditions. In case C, it was found that the scale of the anchor tower caissons and wave defense caissons used in case B had to be significantly increased and, in addition, the line of multi-purpose caissons had to be further reinforced by a second line of inner wave defense caissons 70c. The combination of the transverse support caissons 60c, with their lower profile and transverse ports 64c, and the inner wave defense caissons 70c, with their wave-slamming walls and sloping windward face, constitute a wave over-topping absorption, containment and dispersion sub-system for effectively dispersing the waves overtopping the outer line of wave defense caissons 55c.
The up-scaling of the case C wave defense system is necessary in order to bring the overall mass of the integrated wave defense system up to the level needed to be able to withstand the maximum force winds and waves that can be expected at this deepest of commercial sites under consideration. This site would be subjected to the full force of maximum scale hurricane, typhoon or cyclone winds and waves and/or tsunamis, notably waves that are traveling over the longest fetch and are propelled by the strongest possible winds blowing for the longest possible duration, and are approaching the wave defense system up a relatively steep rise.
As noted previously, it was a failure to understand, and design against, the scale of such maximum level forces that led to the destruction of the 100 foot deep breakwater at Signes, Portugal during its first major Atlantic storm.
The description so far has focused mainly on wave defense systems for location at sites in deeper waters, such as along coastlines or offshore. The modularity of the wave defense systems, and their flexibility for scaling assembly into different configurations, allows them to be readily scaled down and used in shallower waters, such as in gulfs, bays, estuaries, rivers, lakes and the like. In addition, the wave defense systems are designed to be used just as effectively in saltwater environments as in either brackish or freshwater environments.
FIGS. 13a, 13b and 13c are cross-sectional elevational views, drawn to the same scale, of typical integrated wave defense systems under varying hydrodynamic and site conditions and located in relatively shallow, protected waters, such as in gulfs, bays, estuaries, rivers, lakes, etc. The wave defense systems shown in FIG. 13 are typical examples of systems that could be used to provide secure harbors for relatively shallow draft vessels, such as coasters, barges, and river and harbor traffic. On the other hand, the wave defense systems shown in FIGS. 10, 11 and 12 are typical examples of systems that could be used to provide secure harbors for deep draft vessels, such as ocean-going vessels.
The same methodology was used in the calculations determining the design of the systems in FIG. 13 as was used in the design of the systems in FIGS. 10, 11 and 12. The calculations and resulting designs were developed in each case under three sets of varying hydrodynamic and site conditions: minimum, intermediate and maximum.
The primary difference between the deeper water configurations shown in FIGS. 10, 11 and 12 and the shallower water configurations shown in FIG. 13 is that, in the shallower waters, the transverse support caissons 60 and the inner wave defense caissons 70 and 75 are much less likely to be needed, if at all. Most integrated wave defense systems for use in shallower, more protected, waters can be constructed using just ballastable, anchor tower caissons, outer wave defense caissons and multi-purpose caissons scaled to appropriate size. It is also probable that the anchor tower caissons used in shallower waters will be the truncated anchor tower caissons 45 rather than the taller anchor tower caissons 40, and that the outer wave defense caissons 50 will most usually be used rather than the outer wave defense caissons 55 (which are more likely to be used in deeper waters).
FIG. 13a is a cross-sectional side elevation of an integrated wave defense system at a site experiencing minimum site conditions and located at a minimum commercial depth (case D), such as would be encountered by river and harbor traffic, barges, etc. In such shallower, more protected, waters under minimum site conditions, the wave defense system could be provided using only a line of multi-purpose caissons 80d. For purposes of establishing a common scale to allow comparison between FIGS. 13a, 13b and 13c, a barge 92 is shown alongside the multi-purpose caissons 80d, 80e and 80f.
FIG. 13b is a cross-sectional side elevation of an integrated wave defense system constructed at a site experiencing intermediate site conditions and located at an intermediate commercial depth (case E), such as would likely be encountered by coastal vessels, river and harbor traffic, barges, etc. This wave defense system comprises a line of outer wave defense caissons 50e anchored at either end by truncated anchor tower caissons 45e. On the leeward side of the outer line of wave defense caissons and in juxtaposition therewith is an inner line of multi-purpose caissons 80e. Again, for comparison purposes, the barge 92 is shown alongside the caissons 80e.
FIG. 13c is a cross-sectional side elevation of an integrated wave defense system located at a site experiencing maximum site conditions and at a maximum commercial depth (case F), such as would be encountered by larger coastal vessels, as well as river and harbor traffic, barges, etc. In case F, an outer line of outer wave defense caissons 50f is anchored at either end by taller anchor tower caissons 40f, rather than the trucated tower caissons 45e used in case B. An inner line of multi-purpose caissons 80f is provided in juxtaposition with the outer line of wave defense caissons 50f, and a line of quay/dock caissons 90f is placed along the multi-purpose caissons 80f.
To illustrate the versatility and full range of scaling of the modular caissons, reference is made to FIG. 14. FIG. 14 shows the full range of scaling for one type of ballastable caisson, in this case, the multi-purpose caisson 80. FIG. 14 shows the scale of these caissons from maximum use in large, open, deeper bodies of water, such as along coastlines or offshore in the ocean, to minimum use in shallower, more protected waters, such as in bays, estuaries, rivers or lakes.
The cross-sectional side elevations shown in FIG. 14 are all drawn to the same scale and are based on the full range of hydrodynamic and site conditions, including fetch, wind velocity, duration, tide, surge, rise, currents and scour effect. FIG. 14 clearly demonstrates the exponential effect of moving wave defense systems out from shallow, protected waters to deeper, offshore waters in the open ocean, especially systems exposed to maximum hydrodynamic and site conditions.
In designing any wave defense system using sunken caisson technology, careful attention must be given to the possibility of the caissons being toppled over by maximum strength waves, which create large scale lifting and slamming forces and turning moments. There are two basic design considerations, unique to sunken caisson technology, which address this problem--namely, the toppling factor and the penetration factor. These will be described with reference to FIGS. 15 and 16.
The toppling factor is a measure of the capability of a wave defense system to resist toppling or turning over, i.e., a resistance to toppling or overturning. The larger the toppling factor, the more likely a wave defense system is to topple when subjected to maximum wave and wind attack and thus the lower the stability of the overall wave defense system. The penetration factor is a measure of the depth of penetration of the caissons, particularly the anchor tower caissons, into the seabed, lake bed, etc., and is a function of the stability of the overall wave defense system. The larger the penetration factor, the less likely a caisson is to be displaced or dislodged when subjected to maximum wave and wind attack and thus the greater the stability of the overall wave defense system.
The toppling and penetration factors are useful as preliminary design considerations in designing the first model of the wave defense system. As described below, these factors are used initially to select the configuration of the caissons for building test models, approximate the caisson model scale, etc. In the examples depicted in FIGS. 15 and 16, representative values have been chosen for an initial design of a typical wave defense system designed for use against maximum scale wave and wind attack under maximum site conditions.
The toppling factor T of a wave defense system is defined as the ratio of the average height h AV of the wave defense system at a given cross section to the maximum width w MAX of the wave defense system at that cross section, i.e., T=h AV /w MAX , and is a measure of the relative likelihood of a sunken wave defense system being toppled (i.e., being lifted up, overturned and swept away) when under maximum scale wave and wind attack. The calculation of an absolute toppling factor for a wave defense system is quite complex. It is, however, useful to show in general terms, with reference to FIG. 15, a typical example of how a toppling factor can be calculated according to the principles of the present invention.
First, a determination is made as to the depth (D 1 ) at mean low water at the desired site.
Second, a determination is made as to the maximum depth (D 2 ) of water at the desired site, i.e., D 1 +maximum tide+maximum storm surge.
Third, a determination is made as to the height (h) of the maximum design wave just before it arrives at the wave defense system, taking into account the variables described hereinabove for determining maximum wave and wind forces at the desired site. In the typical example shown in FIG. 15, h is taken to be 0.8(±)×D 2 .
Fourth, a determination is made of the height (h 1 ) above the seabed, lake bed, etc. of the breaking crest of this maximum design wave for which the wave defense system is designed, again at a point just before it arrives at the wave defense system. In the typical example shown in FIG. 15, h 1 is taken to be 1/2×h+D 2 .
Fifth, a determination is made, depending on the uses to which the wave defense system is to be put, as to whether to allow significant wave over-topping or no wave over-topping. Based on this determination, the maximum height h 2 of the inner wave defense caissons and/or the multi-purpose caissons in the system is determined as a function of the maximum height h 1 . Namely, if significant wave over-topping is to be allowed, then the maximum height h 2 is set close to the value of h 1 , i.e., h 2 =1.0(±)×h 1 . If no wave over-topping is to be allowed, then the maximum height h 2 is set close to twice the value of h 1 , i.e., h 2 =2.0(±)×h 1 . The system shown in FIG. 15 is designed to allow essentially no wave over-topping and is based on the relation h 2 =1.8×h 1 . A multiplier other than 1.8 can be used, and the value of the multiplier is typically determined based on a first approximation of the amount of wave over-topping to be allowed by the system. In this manner, the maximum height h 2 of the highest and most leeward caissons in the system (typically the inner wave defense caissons and/or the multi-purpose caissons) can be determined.
Sixth, knowing the maximum height h 2 of the highest and most leeward caissons in the system, and following the general engineering design and layout principles described hereinabove, it is possible to undertake the preliminary cross-sectional design of the wave defense system.
Seventh, knowing the preliminary cross section of the wave defense system allows for a determination of the average height h AV of the cross section and the maximum width w MAX of the cross section.
Eighth, the initial toppling factor T of the wave defense system is determined by calculating the ratio h AV /w MAX . The initial toppling factor T for the wave defense system shown in FIG. 15 is calculated as T=h AV /w MAX =0.068(±).
The analysis of similar initial calculations of toppling factors for various configurations of wave defense systems suggests that a toppling factor of less than about 0.14, and in particular less than about 0.07, is indicative of a wave defense system that will have little or no tendency to be toppled under maximum wave and wind attack, and even less tendency to be toppled if the penetration factor for the anchor tower caissons in the system also falls within preferred limits as described below.
The penetration factor P of an anchor tower caisson is defined as the ratio of the depth of penetration p of the anchor tower caisson into the bed to the overall height h of the anchor tower caisson, i.e., P=p/h, and is a measure of relative anchorability of the wave defense system. As in the case of the toppling factor, the calculation of an absolute penetration factor for a wave defense system is extremely complex. It is, however, useful to show in general terms, with reference to FIG. 16, typical example of how a penetration factor for the anchor tower caissons can be calculated in accordance with the principles of the present invention.
First, a determination is made of whether the initial penetration factor for the anchor tower caissons in the wave defense system should be closer to a maximum level or closer to a minimum level. This determination is based on an initial evaluation of the sub-surface conditions of the intended installation site. Most wave defense sytems are likely to be located near or at existing densely populated areas along coastlines or shorelines, and most of these existing coastal population centers tend to be located where the sub-bed conditions often tend towards "soft" materials, such as silts, soft clays, silt/sand mixes, etc. and do not as often tend towards "hard" materials, such as hard clays, etc. It is obvious that the relative penetration of an anchor tower caisson into the bed at a soft site needs to be greater than at a hard site in order for the wave defense systems to have the same relative stability.
Second, a determination is made of the initial amount of penetration p that the anchor tower caissons should have, taking into account sub-bed conditions and soil mechanics calculations, and the overall height h of the anchor tower caissons.
Third, the initial penetration factor P for the anchor tower caissons is determined by calculating the ratio p/h.
FIGS. 16a and 16b are explanatory side elevations of two truncated anchor tower caissons of signficantly different overall height h, both embedded in relatively "soft" bed materials. FIG. 16a shows an anchor tower caisson 145a of greater relative height h and embedded to a greater relative depth into the bed than the anchor tower caisson 145b shown in FIG. 16b. It should be noted, however, that the heights H of both anchor tower caissons above the bed is the same in each case. The initial penetration factor P for the anchor tower caisson 145a is calculated as P=p/h=0.54(±) and that of the anchor tower caisson 145b is calculated as P=p/h 0.27(±).
The calculation of the initial penetration factor in each case gives a preliminary indication, for the engineering design and layout of the overall wave defense system, of the "anchorability" of that system provided by its anchor tower caissons.
All other things being equal (including bed and site conditions, wave and wind forces, etc.), the anchor tower caisson 145a with a penetration factor P=0.54(±) shown in FIG. 16a would have a significantly higher wave defense system anchoring capability than would the anchor tower caisson 145b having a penetration factor P=0.27(±) shown in FIG. 16b.
The analysis of similar initial calculations for various wave defense system configurations suggests that for a wave defense system subjected to maximum wave and wind conditions and maximum "worst case" site conditions, including silt type sub-bed soil conditions, the anchor tower caissons anchoring the system should have a penetration factor P ranging between 0.60(±) and 0.30(±) and, within this range, the higher the penetration factor the better the anchorability.
In summary, the deeper penetration of the anchor tower caissons has, as one of its main objectives, the purpose of limiting to the maximum extent possible, any lateral (sideways) movement of the caissons in the wave defense system. This contrasts to the reinforcement sub-system (of transverse support, inner wave defense and multi-purpose caissons) which has, as one of its main objectives, the purpose of limiting, to the maximum extent possible, any backward movement of the wave defense system, as a whole, when under maximum wave and wind attack.
A wave defense system according to the present invention is designed with the objectives that:
(1) The anchor tower caissons remain in a fixed position, thus limiting any lateral (sideways) movement of the wave defense caissons in the overall wave defense system to no greater extent than the compression capability of the energy absorption fenders, shock absorbers, etc. placed between the individual caissons laterally along the length of the wave defense system.
(2) With the anchor tower caissons fixed and only minor lateral movement in the wave defense caissons possible, the reinforcement sub-system (of transverse support inner wave defense and multi-purpose caissons), due, in large part, to the partially sunken positions of the caissons in the bed, is able to limit any backward movement of the wave defense caissons and of the overall wave defense system to no greater extent than the compression capability of the energy absorption fenders, shock absorbers, etc. placed between the individual caissons across the width of the system from windward to leeward.
As a result, any overall wave defense system, constructed using the principles of the present invention, will remain stale at any site even when subjected to maximum adverse hydrodynamic and site conditions.
It should be stressed that the initial toppling and penetration factors should be treated as relative rather than absolute ratios, having as their main initial uses to assist in the selection of the wave defense system configuration and to reduce the cost of model construction. To assist in the selection process between different sunken caisson wave defense systems that may be candidates for the same site, it is often useful in determining which system to use, especially when all alternative systems are extremely complex, by having a preliminary set of comparative data. After selection of the wave defense system configuration, the determination of the first set of caisson dimensions and the first configuration of caisson modules can be made so that models can be scaled and constructed for use in the hydrodynamic (hydraulic) tank tests. Since the construction of models for such tests is costly, anything that can be done to bring the first set of models as close as possible to final can save a great deal of time and money.
The present invention enables construction of wave defense systems comprised of ballastable, trimmable, modular caissons that can be constructed to a maximum extent under cost-controlled conditions in shipyards or shipyard-type facilities; floated, and then towed out to installation sites; assembled, precisely trimmed and then ballasted down, to form the optimal, single, integrated wave defense system needed for the site in question; and removed, if ever necessary, by being disassembled, ballasted up and towed away. The wave defense systems can be constructed from a limited number of standardized, ballastable, modular caissons, which can be scaled up or scaled down to provide wave defense systems capable of withstanding and overcoming the strongest possible wind and wave conditions, including maximum strength hurricanes, typhoons and tsunamis, and the severest possible adverse hydrodynamic, wind and site conditions including maximum fetch, wind velocity and duration, depth, rise, tidal range, storm surge, currents and scouring.
The ballastable, trimmable, modular caissons can be assembled into a reinforcement sub-system comprised of transverse support caissons and one or more lines of inner wave defense caissons for reinforcing a line of outer wave defense caissons. The modular caissons can also be assembled to form a wave over-topping absorption, containment and dispersion sub-system comprised of inner wave defense caissons and transverse support caissons, for absorbing, containing and dispersing wave energy caused by over-topping. Both sub-systems can be integrated in an overall wave defense system to prevent any residual wave over-topping from reaching the protected area on the lee side of the overall wave defense system and to fully protect this area from the strongest possible winds thus allowing the area to be used for vessels maneuvering at slow speed, docking or anchored, especially those vessels having a relatively high "windage" profile, such as tankers and bulk carriers, car carriers, cruise ships, liquified gas carriers, etc. which together currently represent the largest proportion of all vessels engaged in world trade.
The wave defense systems constructed of modular caissons according to the present invention can withstand those wind and wave conditions which actually exist in most locations throughout the world, along coastlines and in deeper, large open bodies of water, including the open ocean. Such locations are much more likely to face the maximum, and severest, wind and wave conditions rather than the less severe conditions faced by locations in shallower, more protected, waters. The unique modular design of the five, primary caissons can be scaled up or down to meet the wind and wave protection requirements, and site requirements, at the location in question, and only those types of modulues need be used that are essential to meeting the hydrodynamic, wind and site conditions at the selected location.
The integrated wave defense system is entirely environmentally safe and can, due to its modular construction, be removed at the end of its useful life so that the site can be returned to its pre-construction state from an environmental standpoint. Because the modular caissons are ballastable, they can be ballasted up and towed away, either for reuse or destruction, and any residual rock and concrete block armor remaining at the original site can be reconfigured into effective fishing reefs.
While the present invention has been described with reference to wave defense systems per se, it is understood that other, known structures may be used in conjunction with the wave defense systems to make them more effective in actual practice. For example, a wave defense system for protecting an artificial manmade island may, depending on site conditions, be made more effective by the placement of one or more underwater berms on the windward side of the wave defense system. In a similar manner, a wave defense system for protecting a coastline or shoreline against erosion and other wave damage may, depending on site conditions, be made more effective by the placement of one or more underwater berms on the leeward side of the wave defense system, i.e., between the wave defense system and the coastline or shoreline. Such underwater berms would most usually be constructed of properly sized riprap in a manner well known in the art.
The present invention has been described with reference to particular embodiments thereof, and obvious variations and modifications will be readily apparent to those of ordinary skill in the art. The present invention is intended to cover all such obvious variations and modifications which fall within the spirit and scope of the appended claims.
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A modular caisson installation demountably installed at a preselected water site. The modular caisson installation includes a plurality of caissons having tops and bottoms and being individually demountably installed in a predetermined configuration at a preselected water site with the caisson bottoms removably seated on a bed at the preselected water site. The caissons being constructed of one or more floatable sections each being fluid trimmable and fluid ballastable and having means for trimming and ballasting the section with fluid to effect controlled lowering and positioning thereof during formation of the installation and controlled raising and removal thereof by floatation to enable demounting of the installation.
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PRIORITY CLAIM
[0001] This Application claims benefit of priority from U.S. Provisional Application No. 61/891,928, filed on Oct. 17, 2013.
FIELD OF INVENTION
[0002] The present application is in the field of art relating to cyclic bifunctional materials useful as monomers in polymer synthesis and as intermediates generally, and to the methods by which such materials are made. In particular, the present invention pertains to synthesis of nitriles, carboxylic acids, aldehydes, and amines from renewable biomass resources.
BACKGROUND
[0003] In recent years, interest has grown in renewable source-based alternatives for cyclic bi-functional materials that have been prepared conventionally from petroleum or fossil-based hydrocarbons, as petroleum resources become increasingly scarce and costly. As an abundant bio-based or renewable-resource, carbohydrates represent a viable alternative feedstock for producing such materials. Biomass contains carbohydrates or sugars (i.e., hexoses and pentoses) that can be converted into value added products from renewable hydrocarbon sources.
[0004] In recent years, researchers have directed their efforts towards discovering efficacious processes for converting biomass into sustainable feedstock for various versatile organic chemical platforms. When considering possible downstream chemical processing technologies, the conversion of sugars to value-added chemicals is very important. Recently, the production of furan derivatives from sugars has become exciting in chemistry because of the potential for achieving sustainable energy supply and chemicals production.
[0005] As an important intermediate substance, readily made from carbohydrates, the compound 5-(hydroxymethyl)-furan-2-carbaldehyde (HMF) exemplifies a multifaceted substrate. HMF is a suitable starting material for the formation of various furan ring derivatives that are intermediates for chemical syntheses, and as potential substitutes for benzene-based rings compounds that have been derived ordinarily from petroleum resources. Recent developments in large-scale manufacturing technology have permitted HMF to become more available commercially. This advance affords opportunities for various secondary or derivative products to be made, which can increase the potential for value added chemical compounds without incurring inordinate costs. HMF, however, has limited uses as a chemical per se, other than as a source for making derivatives. Moreover, HMF itself is rather unstable and tends to polymerize and or oxidize with prolonged storage. Due to the instability and limited applications of HMF itself, studies have broadened to include the synthesis and purification of a variety of HMF derivatives.
[0006] Catalyzed complete reduction (hydrogenation) of HMF A, such as depicted in Scheme 1, under mild conditions generates THF-diols, also known by their IUPAC names: ((2R,5S)-tetrahydrofuran-2,5-diyl)dimethanol B and ((2S,55)-tetrahydrofuran-2,5-diyl)dimethanol C (collectively regarded as 2,5-bishydroxymethyl-tetrahydrofurans (also referred to herein as bHMTHFs)), in a 90:10 cis:trans diastereomeric mixture.
[0000]
[0000] bHMTHFs are versatile molecules that when modified can serve as a substitute for a variety of structurally analogous molecules that have conventionally been derived from petroleum-based sources.
[0007] Heretofore, research for chemical derivatives using bHMTHFs has received limited attention due in part to the great cost and relative paucity (e.g., ˜$200 per gram commercially) of the compounds. Recently, a need has arisen for a way to unlock the potential of bHMTHFs and their derivative compounds, as these chemical entities have gained attention as valuable glycolic antecedents for the preparation of polymers, solvents, additives, lubricants, and plasticizers, etc. Furthermore, the inherent, immutable chirality of bHMTHFs makes these compounds useful as potential species for pharmaceutical applications or candidates in the emerging chiral auxiliary field of asymmetric organic synthesis. Given the potential uses, a cost efficient and simple process that can synthesis derivatives from bHMTHFs would be appreciated by manufacturers of both industrial and specialty chemicals alike as a way to better utilize biomass-derived carbon resources.
SUMMARY OF THE INVENTION
[0008] The present disclosure describes, in part, a simple and elegant chemical process for the synthesis of oxygenated products, such as acids and aldehydes, or other derivative products, such as amines and nitriles, of cyclic bifunctional molecules made from renewable, bio-based sources such as HMF and/or its reduction product, 2,5-bis(hydroxymethyl) tetrahydrofuran (bHMTHF). In general, the process encompasses: a) derivatizing bHMTHF using a sulfonate to generate a tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate); b) displacing at least a sulfonate leaving group from the tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate) with a nucleophile; and either c) hydrolyzing fully with a strong Brønsted acid having a pKa of ≦0 to generate a di-acid, or d) reducing partially to generate a di-aldehyde, or e) reducing fully to generate a di-amine
[0009] In another aspect, the present inventive concept also encompasses the different cis and trans isomeric precursors or intermediates, and products of the present process:
[0010] When cyanide is used in the nucleophilic displacement of the sulfonate leaving group, one generates THF-2,5-diacetonitriles: 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile A and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile B:
[0000]
[0011] When one oxidizes THF-2,5-diacetonitriles with an acid, one generates THF-2,5-diacetic acids: 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetic acid A, and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetic acid B:
[0000]
[0012] When one reduces selectively THF-2,5-diacetonitriles, one generates THF-2,5-diacetaldehydes: 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde A, and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde B:
[0000]
[0013] When one reduces completely THF-2,5-diacetonitriles, one generates THF-2,5-diamines: 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diethanamine A, and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diethanamine B:
[0000]
[0014] Additional features and advantages of the present purification process will be disclosed in the following detailed description. It is understood that both the foregoing summary and the following detailed description and examples are merely representative of the invention, and are intended to provide an overview for understanding the invention as claimed.
DETAILED DESCRIPTION OF THE INVENTION
Section I.—Description
[0015] The present synthesis process opens a new pathway for potential industrial, large-volume production of either 1) an oxidation product, 2) a partially reduced product, or 3) a fully reduced product from THF-diols. In general, the overall preparation process for the different products involves a three-step reaction sequence. Common to each of the product synthesis, the first two reactions steps generate diacetonitrile variants from THF-diols. The third reaction step can vary depending on the desired products; in particular, when the diacetonitrile species is oxidized, one generates a corresponding di-acetic acid species; when the diacetonitrile is partially or selectively reduced, one produces a corresponding di-aldehyde species; and when the diacetonitrile species is fully or completely reduced, one makes a corresponding diethyl-amine species.
[0016] For instance, according to an embodiment for oxygenated products, as illustrated in Scheme 2, THF-diol is derivatized first by sulfonation; second, the resultant disulfonate is reacted with a nucleophile which displaces a sulfonate leaving group; and third, the resultant di-nitrile is either oxidized or reduced partially to generate, respectively, either a di-acid or di-aldehyde. The process is performed under relatively mild conditions (e.g., about −20° C. or −10° C. to about 150° C., depending on reagents) and produces good yields of better than 50% or 60% conversion of THF-diols into the corresponding acids or aldehydes.
[0000]
[0017] In another embodiment also shown in Scheme 2, following the first two reaction steps, one makes a di-amine, when the di-nitrile species is completely reduced. Scheme 3 illustrates this full reduction step. The process produces a significant yield of more than 50% of the di-amine species.
[0000]
[0018] The THF-diacetonitrile species is a versatile precursor to corresponding THF-diacetic acids, THF-diacetaldehydes, or THF-diamines In particular, the resulting compounds can be, for example: a) 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetic acid and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetic acid, (collectively, THF-2,5-diacetic acids); b) 2,2′4(2R,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde (collectively, THF-2,5-diacetaldehydes); or c) 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diethanamine and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diethanamine (collectively, THF-2,5-diamines).
[0019] It is envisioned that each of these resulting compounds can serve as a chemical platform or feedstock; that is, useful building blocks in various applications, such as polymer synthesis or as a precursor for various other chemical and industrial materials. The fixed chiral centers of these precursors are also attractive features. As these analogs gain more traction as value-added chemicals, novel derivatives thereof, tertiary products will likely be studied further to divulge sui generis properties with industrial potential.
A. Sulfonation
[0020] To generate the disulfonates of bHMTHF in the sulfonation reaction of the present preparation process, one can use a variety of sulfonates, including but not limited to, mesylate (methanesulfonate), CH 3 SO 2 O—
[0000]
[0000] (—OMs); triflate (trifluoromethanesulfonate), CF 3 SO 2 O—
[0000]
[0000] (—OTfs); tosylate (p-toluenesulfonate), CH 3 C 6 H 4 SO 2 O—
[0000]
[0000] (—OTs); esylate (ethanesulfonate), C 2 H 5 SO 2 O—
[0000]
[0000] (—OEs); besylate (benzenesulfonate), C 6 H 5 SO 2 O—
[0000]
[0000] (—OBs), and other alkyl and aryl sulfonates without limitation.
[0021] As the most powerful leaving group, triflates (TfO) are more preferred. This reaction exhibits relatively fast kinetics and generates an activated triflic complex. The reaction is usually conducted at a low temperature, less than 0° C. (e.g., typically about −10° C. or −12° C. to about −20° C. or −25° C.), to control the reaction kinetics more easily. This reaction is essentially irreversible, as the liberated triflate is entirely non-nucleophilic. The triflic complex then reacts readily with the bHMTHF, forming an bHMTHF-triflate with concomitant release and protonation of a nucleophilic base (e.g., pyrimidine, dimethyl-aminopyridine, imidazole, pyrrolidine, and morpholine).
[0022] The tosylate, mesylate, brosylate, benzenesulfonate, ethylsulfonate or other sulfonate species can be as effective as triflate in imparting nucleofuges, and manifesting overall yields that were commensurate with that achieved with triflate. But, these other sulfonates tend to react more slowly in comparison to the triflate. To compensate for this, operations at higher temperatures are typically needed for better yields when using these other species.
[0023] In the reaction of bHMTHFs with sulfonates to corresponding disulfonates, the operative temperature parameters for these other sulfonate species can be from about 0° C. to about 50° C., over a reaction time of at least 5-6 hours, in some examples up to about 24 hours. In some embodiments, the reaction step can be performed at or near ambient room temperature (e.g., about 10° C., 15° C. or 20° C. to about 30° C. or 40° C.; typically about 17° C. or 18° C. to about 22° C., 25° C. or 27° C.), depending on the particular species.
[0024] Overall, the present synthesis process can produce copacetic yields of disulfonates of bHMTHF, as demonstrated in the accompanying examples. The process enables the production of disulfonates of bHMTHF in reasonably high molar yields of at least 50% from the bHMTHF, typically more than 55% or 60%. With proper control of the reaction conditions and time, disulfonates of bHMTHF are produced at yields of ≧70%, typically ≧80% or 90% or better. The THF-diol or HMF starting materials can be obtained either commercially or synthesized from relatively inexpensive, widely-available biologically-derived feedstocks. (For analogous reaction, see, U.S. Provisional Application No. 61/816,847, K. Stensrud, “5-(Hydroxymethyl) Furan-2-Carbaldehyde (HMF) Sulfonates and Process for Synthesis Thereof,” filed Apr. 29, 2013, the content of which is incorporated herein by reference.)
B. Nucleophilic Displacement
[0025] Nucleophilic displacement occurs in at least two parts of the synthesis process. First, as mentioned above during the sulfonation reaction, the bHMTHF release and protonates a nucleophilic base. In an embodiment, the nucleophile is a nitrogen-centered compound, such as pyrimidine, which is used as a base to catalyze the conversion of bHMTHF to its corresponding disulfonate.
[0026] Second, the disulfonates of bHMTHF is reacted with another nucleophile, which according to an embodiment, is a cyanide. (After the diacetonitrile is generated with a cyanide nucleophile, the bHMTHFs themselves can also be referred to as cyanide-derivatized bHMTHFs.) The cyanide species can be a cyanide salt, for example including but not limited to, lithium cyanide, sodium cyanide, potassium cyanide, trimethylsilyl cyanide, cesium cyanide, tetrabutyl ammonium cyanide, tetraethylammonium cyanide, copper (I) cyanide, silver cyanide, gold cyanide, mercury (II) cyanide, zinc cyanide, platinum (II) cyanide, palladium (II) cyanide, cobalt (II) cyanide. Although each of these cyanide species are effective in forming the THF-2,5-diacetonitriles precursor from THF-2,5-disulfonates in high yields (e.g., >85% or 90%), more commonly one would employ the potassium or sodium cyanide, trimethylsilyl cyanide, tetrabutyl ammonium cyanide, silver cyanide, and copper cyanide species, because of cost and availability. In certain examples, KCN is a more favored species, as potassium exhibits greater reactivity as a stronger anion than sodium.
[0027] When reacted with the cyanide the THF-disulfonates convert to a 9:1 diastereomeric mixture of THF-2,5-diacetonitriles. The yield of THF-2,5-diacetonitriles is greater than 70% or 75%, typically ≧80% or 90% or more.
[0028] In the conversion of THF-2,5-disulfonates to corresponding diacetonitriles, the solvent used has a boiling point of at least 75° C. up to about 200° C. This is desired because, as in certain embodiments, the reaction temperatures may span from about 120° C. to about 175° C., typically from about 110° C. to about 150° C., although other temperatures either higher or lower (e.g., about 80° C., 95° C. or 100° C. to about 140° C. or 190° C.; typically about 90° C. or 110° C. to about 130° C. or 150° C., 170° C. or 180° C.) are also possible.
C. Solvent & Operational Conditions
[0029] In the present synthesis process, aprotic solvents are favored, as they let the nucleophile be exposed, with little solvation, and hence enhances Sn2 reactions. In aprotic solvents a greater dielectric constant can help prevent the solvent from reacting with the primary reagents, hence minimizing formation of side-products.
[0030] The reactions of the present synthesis process are conducted in solvents with a relative permittivity ≧ε r 25, typically about 30 or 35. For example, DMSO and DMF exhibit relatively high dielectric constants (e.g., ˜30 or 32). Other solvents with high boiling points and dielectric constants, such as NMP and DMA, are effective in cyanide for sulfonate displacement reactions. The reaction to derivatize of bHMTHF with a sulfonate is performed in a solution of solvent having a boiling point ≧110° C.
[0031] The reactions herein are used in effectuating the quantitative conversion of bHMTHFs to corresponding disulfonates. In certain preferred embodiments, a solvent with dielectric constants of at least 30 or 35 are employed in the conversion of THF-2,5-disulfonates to corresponding THF-2,5-diacetonitriles.
D. Products
[0032] In the third step of the present synthesis process, according to each respective embodiment when the THF-2,5-diacetonitriles is either oxidized or reduced, a 9:1 diastereomeric mixture of cis and trans bHMTHFs is converted to a 9:1 diastereomeric mixture of: THF-2,5-diacetic acids, THF-diacetaldehydes, or THF-diamines
[0033] The oxidative reaction produces corresponding THF-2,5-diacetic acids, such as illustrated in Scheme 4.
[0000]
[0000] THF-2,5-diyl-diacetonitriles are subjected to hydrolysis with a concentrated aqueous Brønsted acid solution that effects the oxidized product. The strong Brønsted acid has a pKa of ≦0, which may include without limitation, for example: aqueous hydrochloric, hydrobromic, hydroiodic, perchloric, sulfuric, p-toluenesulfonic, triflic, methanesulfonic, or benzenesulfonic acids.
[0034] In the conversion of the THF-2,5-diacetonitriles to THF-2,5-diacetic acids, one can operate the reaction at a temperature from about 0° C. to about 100° C. The yield of THF-2,5-diacetic acids from THF-2,5-diacetonitriles is >85% or 90%.
[0035] A second class of product is formed when the THF-2,5-diacetonitriles are reduced partially to the corresponding THF-2,5-diacetaldehyde, through a transformation facilitated by the solvent medium. One can use reaction temperatures of about −78° C. to 110° C. The yield of THF-2,5-diacetaldehyde from THF-2,5-diacetonitrile is ≧50%. According to an embodiment, one can deploy a hindered organo-metalic (e.g., aluminum) hydride to selectively reduce THF-2,5-diacetonitriles to THF-2,5-diacetaldehydes; while in an alternative embodiment, a supported catalyst, such as nickel or palladium, is used. Concentrated formic acid is used as a solvent in the catalytic reduction of THF-2,5 diacetonitriles to THF-diacetaldehydes. The hydrogenation reaction usually involves operating at a hydrogen pressure that does not exceed about 250 psi in a reaction vessel. In an embodiment, an aqueous trifluoroacetic matrix is used as a solvent in the selective reduction of THF-2,5-diacetonitriles to THF-diacetaldehydes.
[0036] THF-diethyl-amines are the third class of compounds generated when the THF-2,5-diacetonitriles are reduced completely. The reaction is conducted with a reaction temperature range of about 0° C. to about 50° C. The yield of diethyl-amines from diacetonitriles can be ≧85% or 90%, usually 92% or greater. Pursuant to one embodiment, an unhindered, organometallic (e.g., lithium) hydride in an inert, water-free matrix is utilized for complete reduction of the THF-2,5-diacetonitriles to the corresponding THF-2,5-diethyl-amines; in another embodiment, a carbon supported palladium catalyst immured in an ethanolic matrix, saturated with hydrogen gas, is effective. The hydrogen pressure in these instances does not exceed about 1200 psi.
Section II.—Examples
[0037] The present synthesis system is further illustrated in the following examples for making the A) di-acetic acid, B) di-acetaldehyde, and C) diethyl-amine products.
A. Synthesis of THF-2,5-Diacetic Acid Isomers
[0038] Example 1, demonstrates one approach for synthesizing 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetic acid 4a and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetic acid, 4b
[0039] Step 1: Synthesis of ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(trifluoromethanesulfonate) 2a, and ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(trifluoromethanesulfonate) 2b.
[0000]
[0040] Experimental: An oven dried, 25 mL single-neck round bottomed flask equipped with a ½″×⅛″ tapered PTFE coated magnetic stir bar was charged with 226 mg of THF-diols 1 (1.71 mmol), 410 μL of pyridine (˜3 eq.) and 10 mL of anhydrous methylene chloride. The neck was capped with a rubber septum and a needle affixed to an argon inlet and the flask immersed in a saturated brine/ice bath (−10° C.). While stirring and under an argon blanket, 574 μL of triflic anhydride (3.42 mmol) was added dropwise over a 15 minute period. After complete addition, the flask was removed from the ice bath, warmed to ambient temperature, and the reaction continued for 2 more hours. After this time, an aliquot was removed and a portion spotted on a silica gel thin-layer chromatography plate abutting a spot from the THF diol starting materials for comparison. The plate was developed using a 100% ethyl acetate eluent, and after staining with cerium molydate, the product mixture revealed one distinct spot, R fl =0.67 (THF-diol ditriflate). No band was observed at the baseline (R f =0), indicating that all the THF-diol reagent had been converted. Solids were the filtered and the solvent removed under reduced pressure, affording 666 mg of 2a, 2b a yellow, viscous oil (98% of theoretical). 1 H NMR (CDCl 3 , 400 MHz, salient cis isomer, 2a) δ (ppm) 4.58 (m 2H), 4.47 (m, 2H), 4.44 (m, 2), 4.32 (m, 2H), 2.15 (m, 2H), 1.87 (m, 2H); 13 C NMR (CDCl 3 , 100 MHz salient cis isomer) δ (ppm) 120.44, 84.2, 73.5, 30.3
[0041] Step 2: Synthesis of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile 3a, and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile 3b.
[0000]
[0042] Experimental: An oven dried An oven dried, 25 mL single-neck round bottomed flask equipped with a ½″×⅛″ tapered PTFE coated magnetic stir bar was charged with 650 mg of 2a and 2b (1.64 mmol), 161 mg of sodium cyanide (3.28 mmol), and 5 mL of anhydrous DMSO. The reaction was stirred vigorously overnight. After this time, an aliquot was removed and a portion spotted on a silica gel thin-layer chromatography plate abutting a spot from the 2a, 2b for comparison. The plate was developed using a 50% ethyl acetate in hexanes as the eluent, and after staining with cerium molybdate, the product mixture revealed one distinct spot, R fl =0.58 (THF-diol ditriflate). No band was observed at R f =0.41, corresponding to 2a, 2b, indicating that these reactants had been entirely converted. The solution was transferred to a 50 mL separatory funnel and diluted with 15 mL of methylene chloride and 25 mL of water. The organic layer was extracted, dried with anhydrous sodium sulfate, and concentrated, under reduced pressure, furnishing 222 mg of 3a, 3b as a pale yellow oil (90% of theoretical). 1 H NMR (CDCl 3 , 400 MHz, salient cis isomer, 3a) δ (ppm) 3.92 (m 2H), 2.98 (m, 2H), 2.81 (m, 2H), (m, 2H), 2.01 (m, 2H), 1.77 (m, 2H); 13 C NMR (CDCl 3 , 100 MHz salient cis isomer) δ (ppm) 114.23, 69.8, 30.2, 20.1.
[0043] Step 3: Synthesis of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetic acid 4a and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetic acid, 4b
[0000]
[0044] Experimental: A 25 mL round bottomed flask equipped with an octagonal magnetic stir bar was charged with 200 mg of 3a, 3b (1.33 mmol), and 10 mL of 3N aqueous HCl. The mixture was stirred vigorously for 2 h, after which time an aliquot was removed and analyzed by 13 C NMR (400 MHz, d 6 -DMSO). A salient signal at 173.4 ppm coupled with the absence of signature nitrile signal at 114.23 ppm was cogent proof that full conversion had occurred. Excess solvent was then removed in vacuo, affording 231 mg of 4a and 4b as beige solid (92%). 1 H NMR (D 2 O, 400 MHz, salient cis isomer, 4a) δ (ppm) 4.01 (m 2H), 2.42 (m, 2H), 2.19 (m, 2H), (m, 2H), 1.90 (m, 2H), 1.61 (m, 2H); 13 C NMR (D 2 O, 100 MHz salient cis isomer) δ (ppm) 171.3, 76.5, 40.2, 30.6.
[0045] Example 2, demonstrates an iteration using an alternate sulfonate species, cyanide reagents, and/or solvents.
[0046] Step 1. Synthesis of ((2R,55)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(4-methylbenzenesulfonate) and diastereomer
[0000]
[0047] Experimental: An oven dried, 25 mL single-neck round bottomed flask equipped with a ½″×⅛″ tapered PTFE coated magnetic stir bar was charged with 300 mg of THF-diols 1a and 1b (2.27 mmol), 866 mg of p-toluenesulfonyl chloride (tosyl chloride, 4.54 mmol), 550 μL of pyridine (˜3 eq.), 2.7 mg of dimethylaminopyridine (DMAP, 0.227 mmol) and 10 mL of anhydrous methylene chloride. The neck was capped with a rubber septum and a needle affixed to an argon inlet stirred vigorously overnight under an argon blanket. After this time, the solution was transferred to a 100 mL separatory funnel, diluted with 20 mL of methylene chloride, and washed three times with 10 mL of a 1N aqueous HCl solution. After each washing, the aqueous layer was removed, and residual organic phase dried with anhydrous magnesium sulfate then concentrated, after filtration, under reduced pressure, affording 922 mg of a light yellow solid, representing ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(4-methylbenzenesulfonate) and diastereomer (92% of theoretical). 1 H NMR (CDCl 3 , 400 MHz, salient cis isomer) δ (ppm) 7.79 (d, J=8.0 Hz, 2H), 7.39 (d, J=8.0 Hz, 2H), 4.36 (m, 2H), 4.33 (m, 2H), 4.21 (m, 2H), 2.51 (s, 6H), 2.11 (m, 2H), 1.80 (m, 2H); 13 C NMR (CDCl 3 , 100 MHz salient cis isomer) δ (ppm) 146.7, 142.6, 132.1, 129.3, 84.0, 72.5, 30.6, 22.1
[0048] Step 2. Synthesis of 2,2′-((2R,55)-tetrahydrofuran-2,5-diyl)diacetonitrile and diastereomer
[0000]
[0049] Experimental: An oven dried, 25 mL single-neck round bottomed flask equipped with a ½″×⅛″ tapered PTFE coated magnetic stir bar was charged with 700 mg of ((2R,55)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(4-methylbenzenesulfonate) and diastereomer (1.59 mmol), and 5 mL of anhydrous DMF. The flask was capped with a rubber septum affixed to an argon and, while stirring and under argon, 438 μL of trimethylsilyl cyanide (3.50 mmol) was injected dropwise. The septum was then replaced with a reflux condenser attached to an argon inlet, and solution stirred vigorously at 150° C. overnight. After this time, an aliquot was removed and a portion spotted on a silica gel thin-layer chromatography plate abutting a spot from the THF diol starting material for comparison. The plate was developed using a 50% ethyl acetate in hexanes as the eluent, and after staining with cerium molybdate, the product mixture revealed one distinct spot, R fl =0.58 (THF-diol ditriflate). No band was observed at R f =0.41, corresponding to reactants, indicating that these had been entirely converted. The solution was transferred to a 50 mL separatory funnel and diluted with 15 mL of methylene chloride and 25 mL of water. The organic layer was extracted, dried with anhydrous sodium sulfate, and concentrated, under reduced pressure, furnishing 216 mg of a 2,2′4(2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile and diastereomer as a pale yellow oil (91% of theoretical). 1 H NMR and 13 C NMR spectra were consistent with those described previously.
[0050] Step 3. Synthesis of 2,2′4(2R,5S)-tetrahydrofuran-2,5-diyl)diacetic acid and diastereomer
[0000]
[0051] The same reaction provisions to prepare these compounds were as previously detailed.
[0000] B. Synthesis of THF-2,5-dicarbaldehydes by Partial Reduction of THF-2,5-dinitriles
[0052] The process for making dicarbaldehydes is similar to that described for the diacids, until the third reaction step. Instead of oxidization, the THF-2,5-dinitrile is partially reduced. The following examples demonstrate some different approaches to convert the diacetonitrile to a corresponding aldehyde.
Example 1
[0053] Conversion of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile and diastereomer to 2,2′4(2R,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde and diastereomer using diisobutylaluminum hydride at low temperature.
[0000]
[0054] Experimental: A flame-dried, 25 mL round bottomed flask equipped with a magnetic stir bar was charged with 200 mg of a 9:1 mixture of 2,2′-((2R,55)-tetrahydrofuran-2,5-diyl)diacetonitrile 1a and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile 1b (1.33 mmol) and 10 mL of anhydrous dichloromethane. The flask was capped with a rubber septum affixed to an argon inlet, then immersed in a saturated dry ice/acetone slurry (−78° C.). While stirring and under argon, 1.33 mL of a 1 M diisobutylaluminum hydride solution in methylene chloride was added dropwise over 5 min and the reaction continued at −78° C. for 1 hour. After this time, the dry ice/acetone bath was removed, and reaction was quenched with a minimum amount of water. Solids were filtered, and the permeate concentrated in vacuo over 72 hours, producing a 198 mg of a clear, colorless oil (95% of theoretical). 1 H NMR (400 MHz, CDCl 3 , salient cis product) δ (ppm) 9.75 (m, 2H), 4.02 (m, 2H), 2.71 (m, 2H), 2.33 (m, 2H), 1.84 (m, 2H), 1.57 (m, 2H); 13 C NMR (100 MHz, CDCl 3 , salient cis product) δ (ppm) 198.4, 73.2, 50.7, 29.7.
Example 2
[0055] Synthesis of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde and diastereomer from 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile and diastereomer using Raney Nickel in formic acid.
[0000]
[0056] Experimental: A 100 cc round bottomed flask equipped with a magnetic stir bar was charged with 1 g of a 9:1 mixture of 2,2′-((2R,55)-tetrahydrofuran-2,5-diyl)diacetonitrile 1a and 2,2′4(25,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile 1b (6.66 mmol), 2 g of Raney nickel, and 50 mL of ˜88% formic acid. The flask was then outfitted with an Allihn condenser and the mixture heated to reflux for 2 h. After this time, the solution was cooled to ambient temperature, then vacuum filtered using a Buchner funnel The remnants were then concentrated under reduced pressure over 48 hours, resulting in a loose, colorless oil, that was then suspended in water and heated to a boil for 30 min. After this time, excess water was removed and the crude product charged to a pre-fabricated silica gel column, which effectively sequestered 586 mg of the title compounds 2a and 2b (56% of theoretical) as clear, colorless oils using a hexanes/ethyl acetate gradient mobile phase (50% to 100% ethyl acetate). 1 H and 13 C NMR were congruent with the aforementioned product analysis delineated in Example 1, above, of the aldehyde conversion.
Example 3
[0057] Partial catalytic reduction of 2,2′4(2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile and diastereomer to 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetaldehyde and diastereomer under mild, hydrolytic conditions.
[0000]
[0058] Experimental: A 250 cc Hasteloy autoclave with an overhead stirrer was charged with 2 g of a 9:1 mixture of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diacetonitrile 1a and 2,2′-((25,55)-tetrahydrofuran-2,5-diyl)diacetonitrile 1b (13.32 mmol), 1 g of 10% Pd/C, and 50 mL of a 50% aqueous trifluoroacetic acid (TFA) solution. The vessel was sealed, purged ×3 with volumes of H 2 corresponding to 250 psi then pressurized with H 2 until the gauge read 200 psi. The mixture was stirred at 40° C. overnight at room temperature, after which time the excess catalyst removed by vacuum filtration, and residual solution evaporated under reduced temperature, affording a colorless, loose crude oil. This was diluted with a minimal amount of methylene chloride and charged to a prefabricated silica gel column which effectively sequestered 1.02 g of the title compounds 2a and 2b (49% of theoretical) as clear, colorless oils using a hexanes/ethyl acetate gradient mobile phase (50% to 100% ethyl acetate). 1 H and 13 C NMR were congruent with the aforementioned product analysis delineated in Example 1.
[0000] C. Synthesis of THF-2,5-diamines by Complete Reduction of THF-2,5-diacetonitriles
[0059] As with the foregoing examples relating to oxygenated products, THF-diol is first subjected to sulfonation and derivatized. The resulting THF-sulfonate is then reacted with a nucleophile, such as cynide, to generate a diacetonitrile species. The following presents embodiments of the diamine synthesis process, which has two viable pathways to complete reduction of the diacetonitrile species.
[0060] Ex. Route 1: Synthesis of 2,2′-((2R,5S)-tetrahydrofuran-2,5-diyl)diethanamine 2a and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diethanamine 2b from bHMTHFs 1a and 1b using a metal hydride.
[0000]
[0061] Experimental: A flame-dried, single necked 10 mL round bottomed flask equipped with a PTFE coated magnetic stir bar was charged with 125 mg of a 9:1 mixture of 1a and 1b (0.832 mmol) and 5 mL of anhydrous THF. The homogeneous mixture was cooled to −10° C. in a saturated brine/ice bath, and, while stirring, 1.67 mL of a 1M solution of lithium aluminum hydride in THF (LAH) was added dropwise over 10 min (1.67 mmol). After complete addition, the ice bath was removed and reaction continued at room temperature for 2 h. After this time, solids were filtered, and the filtrate washed with 2 mL of a 0.5M HCl solution. Excess solvent was then removed in vacuo, affording 121 mg of 2a and 2b as a light yellow syrup (92% of theoretical). 1 H NMR (400 MHz, CDCl 3 , salient cis signals) δ (ppm) 4.95 (s, 4H), 3.51 (m, 2H), 2.79 (m, 4H), 2.03 (m, 2H), 1.70-1.67 (m, 6H); 13 C NMR (100 MHz, CDCl 3 , salient cis signals) δ (ppm) 80.8, 40.5, 37.9, 32.0 ppm.
[0062] Ex. Route 2: Synthesis of 2,2′-((2R,55)-tetrahydrofuran-2,5-diyl)diethanamine 2a and 2,2′-((2S,5S)-tetrahydrofuran-2,5-diyl)diethanamine 2b from bHMTHFs 1a and 1b via catalytic hydrogenation.
[0000]
[0063] Experimental: A 300 cc stainless steel Parr reactor vessel was charged with 250 mg of a 9:1 mixture of 1a and 1b (1.65 mmol), 200 mg of 10% Pd/C and 100 mL of absolute ethanol. The vessel was affixed to the reactor apparatus, sealed, purged ×3 with volumes equal to 1000 psi of hydrogen gas (H 2 ), and pressurized to 1200 psi with H 2 . While overhead stirring at 500 rpm, the hydrogenation reaction proceeded for 2 h at room temperature. After this time, solids were filtered, and surplus solvent removed under reduced pressure, affording 258 mg of 2a and 2b as a clear, viscous oil (98% of theoretical). 1 H NMR (400 MHz, CDCl 3 , salient cis signals) δ (ppm) 4.95 (s, 4H), 3.51 (m, 2H), 2.79 (m, 4H), 2.03 (m, 2H), 1.70-1.67 (m, 6H); 13 C NMR (100 MHz, CDCl 3 , salient cis signals) δ (ppm) 80.8, 40.5, 37.9, 32.0 ppm.
[0064] The present invention has been described in general and in detail by way of examples. Persons of skill in the art understand that the invention is not limited necessarily to the embodiments specifically disclosed, but that modifications and variations may be made without departing from the scope of the invention as defined by the following claims or their equivalents, including other equivalent components presently known, or to be developed, which may be used within the scope of the present invention. Therefore, unless changes otherwise depart from the scope of the invention, the changes should be construed as being included herein.
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A simple and elegant chemical process for the synthesis of oxygenated products, such as acids and aldehydes, or other derivative products, such as amines and nitriles, of cyclic bifunctional molecules made from renewable, bio-based sources such as HMF and/or its reduction product, 2,5-bis(hydroxymethyl)-tetrahydrofuran (bHMTHF) is described. In general, the process involves: a) generating a tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate) from bHMTHFs using a sulfonate; b) displacing nucleophilically at least a sulfonate leaving group from the tetrahydrofuran-2,5-diyl-bis(methylene)-bis(sulfonate) to form a THF-dinitrile; and either c) oxidizing the THF-dinitrile with an acid having a pKa of ≦0 to generate a di-acid, or d) reducing partially the THF-dinitrile to generate a di-aldehyde, or e) reducing fully the THF-dinitrile to generate a di-amine.
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This is a continuation of Ser. No. 07/829,810 filed Feb. 3, 1992, now abandoned which is a continuation-in-part of the copending application of the same title, Ser. No. 07/594,729, filed Oct. 9, 1990 now abandoned.
BACKGROUND OF THE INVENTION
Accurate measurement of wastewater flows in sewers and other open channels is increasingly important for both economic and environmental reasons. Existing flowmeters for open channels are of two types: head-type meters which measure water depth and are used with weirs and flumes; and velocity-area (VxA) meters which obtain flow cross section area from a measurement of depth and multiply this area by a factor based on a measurement of water velocity. Properly installed head-type meters are 1-2% accurate; VxA meters are typically at least an order of magnitude less accurate, but can be used where installation of a flume or weir is impractical or impossible.
The common weakness of VxA meters is in the measurement of water velocity. Techniques commonly used for wastewater velocity measurement are contrapropagating and reflective ultrasonics (both based on frequency shifting), electromagnetic probes, and (for short-term measurements) paddlewheels and turbines. Such devices are typically rated for velocity ranges to 30 fps (feet per second) and higher; accuracy is severely degraded at low velocities. The velocities found in open channel wastewater flows range from typical highs of 3 to 5 fps in free flow down to zero or even reverse flow under stoppage conditions.
In open channel flow applications, present velocity-measuring instruments are at best operating in the bottom 10-15% of their full range, with resulting poor accuracy. Electromagnetic probes are especially prone to fouling, with resultant calibration drift, in slowly moving flows. In wastewater flows, paddlewheel, turbine, target and other intrusive sensors typically fail in short times due to fouling and trash accumulation. There is a great need for an open channel flowmeter for wastewater which can operate accurately in pipes and channels (without using a weir or flume) which is not subject to the shortcomings of velocity measurements.
Several manual techniques are in common use for measuring water flowrate in channels without measuring velocity. These methods measure the movement of the water along the channel over a measured distance in a measured time, as contrasted with measuring the instantaneous water velocity at the location of the velocity sensor. The simplest of these techniques is the method of floats; small floats are dropped into the flow and visual measurements are taken of the travel time to a known point downstream. The water flowrate is computed as: ##EQU1## It is possible to compute a value for "average" velocity, dividing the travel distance by the travel time. The result is a fictitious value, which for most situations will not be the actual velocity of any significant portion of the flow. Regardless, this "average velocity" is a derived value; it is not a measurement, and it not required for the calculation of flowrate.
The same principle underlies dye and salt techniques. Dye may be dumped into moving water, and the time of travel observed visually. Salt may be dumped into the water, and the time of arrival at the downstream point observed with a conductivity meter. These techniques are characterized by low resolution in distance and time measurements, requiring the measurements to be made over large distances and times; rapid changes of flowrate are averaged out rather than measured. Also, for each measurement, material must be added to "tag" the water. On the positive side, the lack of velocity measurement means these techniques work equally well, though inaccurately, in both fast and slow flows. To date, this benefit has not been realized in an automated instrument because of these problems of the long baseline and need to continuously add "tagging" material.
The present invention solves these problems by using the solids already being carried by the flowing water, and by providing a precise, short-baseline method for accurately measuring the travel distances of such solids. The invention successively identifies and measures the location of individual solids at short time intervals and calculates the liquid flowrate based on the movement of these solids. Because solids are carried throughout the flow, the technique measures throughout the cross section of flow; accuracy is not dependent on laboratory-quality flow conditions. The present invention is also useful in flows without measurable solids by introducing bubbles in the flow.
Accordingly, the first object of the invention is to implement a channel flowmeter to continuously measure flowrate by measuring water movement instead of velocity.
Another object of the invention is to measure the water movement using short baselines and short times, for installation convenience and to better track short-term variations in flowrate.
Another object of the invention is to perform such non-velocity flow measurements without the addition of tagging material to the flowing water.
Another object of the invention is to take measurements throughout the flow, preserving accuracy where flow conditions are irregular.
Another object of this invention is to provide a volumetric flowmeter which accurately computes a true flow volume regardless of flow velocity, does not require a known flow profile, and is essentially independent of upstream and downstream flow conditions, including flow stoppages.
Another object of this invention to provide a volumetric flowmeter which can be used in the same applications as velocity-area meters, but which avoids the shortcomings of velocity measurement.
Another object of this invention is to provide an accurate method of measuring flowrates of object-bearing liquids moving slowly.
SUMMARY OF THE INVENTION
Broadly speaking, the flowmeter of this invention computes the volumetric flow rate of a liquid by measuring the changing positions of objects carried in the flow. This information can be combined with data describing the size, shape and fraction of filling of the conduit. By measuring displacement instead of velocity, accurate measurements of liquid movement can be obtained even when flows are moving very slowly, or not at all.
Objects carried in flowing liquids tend to be distributed through the flowing liquid, so object travel measurements can be taken at many points in the cross section of flow. Using echo-ranging techniques, object positions can be measured remotely from the sensor, and thus moving a sensor to each measurement point (the traditional method for multipoint measurement using velocity meters) is not required.
While the method may be implemented using a variety of techniques, the implementation described is constructed using ultrasonic echo-ranging transducers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration in block diagrammatic form of one embodiment of a flowmeter constructed in accordance with the principles of this invention.
FIG. 2 is an illustration in sectional view of a fluid motion sensor and showing a technique used in this invention for the determination of distance to an object in the measured liquid.
FIG. 3 is an illustration of the echo patterns returned by successive scans showing a technique of identifying echoes from individual objects in the flow.
FIG. 4 is an illustration in sectional perspective view of the flow within a conduit being measured using the method of this invention.
FIG. 5 is an illustration in isometric view of one type of ultrasonic transducer array used for control of directional sensitivity in this invention.
FIG. 6 is an illustration in sectional view of an ultrasonic sensor mounted so as to minimize disturbance of the passing flow, while operating in accordance with the principles of this invention.
FIG. 7 is an illustration in sectional form of a metering flume with liquid depth and motion sensors mounted in accordance with this invention.
FIG. 8 is an illustration in sectional view of a fluid motion sensor arranged as an insertable probe into a closed conduit, in accordance with the principles of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is illustrated one embodiment of the basic elements of a flowmeter of this invention designed to measure open channel flow, i.e., flow in a conduit in which the flow depth is variable. A sensor holder 1 is located near the bottom of a conduit 2 of known size and shape. In the illustrated embodiment, both sensor 3 and sensor 4 are piezoelectric crystals which emit pulses of ultrasonic energy in response to voltage variation in their respective electrical cables 5 and 6. Returning ultrasonic energy striking either sensor 3 or sensor 4 is converted to an electric voltage signal, which is transmitted to transceiver 7 through cable 5 or cable 6, respectively. Transceiver 7 is controlled by computer means 8.
In operation, transceiver 7 causes liquid depth sensing piezoelectric crystal 3 to emit ultrasonic energy upwards toward the liquid surface 9, from which some of the ultrasonic energy is reflected back downward. The returning ultrasonic energy generates a voltage in liquid depth sensing crystal 3, which voltage is transmitted to transceiver 7 through cable 5. Transceiver 7 transmits a voltage signal through connection 10 to Timer/Counter 11, which in the described embodiment is integrated into computer means 8. The physical arrangement of computer means 8 is not significant to the principles of this invention.
Counter-timer 11 converts the interval between transmission and reception of ultrasonic energy ("echo time") into data for use by computer 8. Computer 8 adjusts the echo time data for temperature effects and then computes distance from sensor 3 to liquid surface 9, using preprogrammed values for propagation velocity. To this computed distance, the computer adds offset 12 of sensor 3 above the invert of conduit 2 to produce a value corresponding to depth of liquid 13 in conduit 2. Having this depth, computer 8 then computes the cross-section area of flowing liquid 13 using preprogrammed data for shape and size of conduit 2.
In applications where a conduit will always be flowing full, often referred to as "closed-pipe" flow, liquid depth sensor 3 is not required, and the flow cross-section area of liquid 13 is presumed to be identical to the cross-section area of conduit 2.
Object travel sensor 4 is also a piezoelectric crystal but is oriented at angle 14 to the direction of flow. Sensor 4 emits ultrasonic energy in response to voltage signals from transceiver 7. Objects 15 and 16, representative of various solid and semisolid objects or bubbles carried by flowing liquid 13, pass through the beam 17 of ultrasonic energy emitted by sensor 4. Some of this ultrasonic energy reflected by objects 15 and 16 strikes sensor 4 and is converted to voltage signals which are returned to transceiver 7 through cable 6. Transceiver 7 supplies distance-related electronic signals to Counter/Timer 11, which in turn produces distance data to computer 8. Computer 8 applies trigonometric corrections for beam angle 14 to calculate displacement of objects 15 and 16 in the direction of flow of liquid 13.
The word "sensor" as used in this disclosure refers to a combination of transducers used to emit and detect ultrasonic energy. A sensor may be a single transducer used as both transmitter and receiver; it may also be constructed as separate transducers which may be collocated or at separated locations. Computer 8 causes the above-described process to reoccur at short time intervals, typically 2-5 times per second.
Because of the nature of sewage (transporting many solids) and the opportunistic nature of these measurements, computer means 8 includes software techniques for processing multiple echo returns and identifying the same object in successive scans. While these techniques are similar in fundamentals to tracking techniques used in radar and sonar systems, the special nature of this application requires unique implementations of these techniques.
The first major difference is that radars and sonars work in the "far field" zone; the target is sufficiently far away that it is essentially at the same distance from all parts of the antenna. Phase cancellation effects are negligible, and the plot of radiated intensity vs. angle from beam center is reasonably smooth. Radars and sonars use this smooth angular graduation of intensity to obtain directional information.
In the present invention, a transducer diameter of less than 1" and required working distances in the range of 4 to 20 inches result in the transducers working in the "near zone" where phase cancellation effects produce an irregular plot of radiation intensity vs center angle. Directional information cannot be obtained from echo strength.
The second major difference is that radar antennae are usually able to rotate, thus allowing both tracking of the target and comparisons of returns at different angles, whereas in the present invention the sensor orientation is typically fixed.
The third major difference is in opportunity for observation. Radar operates at almost light speed and typically can take many scans of a target before the target moves significantly; measurements can be repeated as needed. Wastewater solids or bubbles passing the present flowmeter may be in the window of measurement for less than one second; ultrasound travels 500,000 times slower than light; the targets typically move between scans. The result is that the opportunity for repeat measurements is not available.
Fortunately, a fourth major difference provides great simplification for the present invention: unlike radar or sonar, not every solid or bubble has to be identified and measured. If a travel measurement of one object does not validate, another opportunity will soon arise.
The present invention identifies passing objects using a straight forward procedure. Refer to FIG. 2, in which successive positions 15a-15e and 16a-16e are shown for two transported objects 15 and 16. Refer also to FIG. 4, in which are shown demodulated data corresponding to scans 19a-19e taken at times corresponding to object positions a-e. The target identification procedure is:
1. Scan 19a is empty, because no objects are within ultrasonic beam 17.
2. Scan 19b contains sharp-edged transitions 20 and 21 defining echo 22b returned from object 16; object 15 has not yet entered ultrasonic beam 17 and so is invisible to sensor 4. The time to leading edge 20 corresponds to the distance to object 16, and the time between leading edge 20 and falling edge 21 corresponds to the size and reflectivity of object 16. Computer means 8 tentatively identifies echo 22b.
3. Computer means 8 causes scan 19c to be taken and creates "data window" 23c, of size and position based on previously taken data if available, or otherwise on general hydraulic principles. Computer 8 then searches window 23c for an echo of similar size to echo 22b in previous scan 19b.
In scan 19c, echo 23c satisfies this test. The presence of echo 24c from object 15 does not interfere with this test, even if inside window 22.
4. Computer 8 causes scan 19d to be taken, applies a smaller window 23d based on distance and size information from scans 19b and 19c, and verifies the presence of suitable echo consistent with previous data, even though leading edge of echo 22d has been masked by echo 24d.
5. Computer 8 causes scan 19e to be taken. Object 16 has moved out of ultrasonic beam 17 and is no longer visible. Echo 24e is significantly shorter than echoes 22b-22d and is identified by computer 8 as not corresponding to the same object as echoes 22b-22d.
6. Computer means 8 then processes echo times from object 16 into displacements taking into account the trigonometric effects of beam tilt angle 14, and combines time interval, temperature and other preprogrammed data to determine the movement of the liquid.
Computer means 8 controls the effectiveness of echo-ranging by adjusting both the strength of transmission and the sensitivity of detection. Where many objects of varying sizes are simultaneously within ultrasonic beam 17, computer 8 thus can reduce the number of objects detected to a number manageable by an 8-bit microprocessor in a reasonably short time.
Any ultrasonically reflective object travelling with the flow will permit measurements; if sufficient solid objects are not present, bubbles may be introduced into the flow, and effects of bubble rise compensated for in the calculations. Unlike traditional "tagging" methods, in this case the "tagging" material is readily available, inexhaustible and free, requiring only a small, low-power pump to use. In the context of this invention, a bubble is considered to be an "object" because, like a solid, it creates a discontinuity in the liquid which is detected by the sensor.
It is not necessary to determine the actual position of individual objects in the flow to compute the movement of the liquid. Because such objects are randomly distributed throughout the flow, any calculation method which assigns equal weight to each measurement will produce accurate results, provided the ultrasonic beam covers either substantially all of the cross section of flow, or a representative portion thereof. The simplest method is to base the flowrate calculation for the entire cross-section upon the latest travel measurement, using the data from each measured object only until the next measurement is taken; the raw data output will show sharp fluctuations but can be smoothed in the computer means. Other methods of smoothing the data are to retain all measurements for a defined period (for example, the preceding 5 seconds) or to retain some fixed number of the most recent measurements; the calculated flowrate is then based on the aggregate of retained measurements. FIG. 3 shows one embodiment of the invention with sensor holder 1 located on the bottom of conduit and with ultrasonic beam 17 illuminating a substantial portion of the flow cross section.
The calculation techniques described above presume that sensor 4 is able to "see" most of the cross-section of the flow. If the flow conduit is substantially the same in both cross dimensions (circular or square), this condition can be adequately satisfied using only one sensor. If the flow conduit is substantially elongated in cross section (wide shallow flows or narrow deep flows), provision may be included to increase the monitored portion of the flow. One such technique is to use an array of divergently pointing sensors. A second technique is shown in FIG. 5, where sensor 4 is subdivided electrically into one or more segments 25 and 26; such segments may be operated to include electronic phase-shifting to change the direction of sensitivity of sensor 4 without physically rotating it. This technique is well known to those skilled in the art of ultrasonic transducers (and in antenna design in general) as "steering the beam". Using this technique, a single fixed sensor can be readily made to "sweep" across the cross-section area of flow.
Computer 8 calculates volumetric flow rate of liquid 13 according to the equation: ##EQU2## This equation is based on three measurements of distance--one of liquid depth for flow area, and two of distance to an object moving in the stream--and one measurement of time. Such ultrasonic distance measurement is typically accurate to about 0.030" and the object travel is typically measured over about 12", so travel measurement accuracies of 0.5% are easily obtained. Because velocities of moving liquids are small compared to the velocity of sound in such liquids, the accuracy of distance measurement is not significantly affected by velocity, and flow measurement accuracy is maintained at all velocities.
Ideally, the presence of sensor holder 1 should not distort the measured flow. Referring to FIG. 6, this condition can be approximated by minimizing the slope of the upstream face 27 of sensor holder 1. However, ultrasonic beam 17 is emitted approximately perpendicular to sensor 4. To avoid inserting face 27 as a near-perpendicular obstruction into the flow, face 27 may be constructed as a wedge 28 of acoustically-transmissive material. The direction of ultrasonic beam 17 is altered by passage through wedge 28 according to Snell's law of refraction. Computer 8 can then compensate for such change of direction. Also, if the sonic propagation velocity in wedge material is substantially the same as in measured liquid 13, the direction of ultrasonic beam 17 will not be significantly changed by passage through wedge 28.
The present invention may be applied to the invention of U.S. Pat. No. 4,480,466 by the same author, replacing the commercially available liquid velocity measuring technique incorporated into that invention. The prior invention can then be programmed to discriminate between normal and submerged flow conditions by comparison of flowrates instead of velocities. In FIG. 7, liquid travel sensor 4 has been incorporated into leading edge 30 of raised throat section of metering flume 29. Wedge 28 has been shaped to match leading edge 30 for minimum distortion of flow. Liquid depth sensor 3 can then be mounted flush with bottom of flume 29, instead of raised into the flow as shown in the cited previous invention.
FIG. 8 illustrates another embodiment of the principles of this invention as applied to flow measurement in closed conduits. Conduit 31 is fitted with port 32 for the entrance of probe 33, which is slanted downstream to shed waterborne trash. Lower end of probe 33 contains liquid motion sensor 4 and wedge 28 mounted to point upstream. Ultrasonic beam 17 is thus directed upstream to detect reflective objects and compute flowrates as described above using the size and shape of the conduit. This embodiment of the invention may be further modified by the inclusion of a liquid depth sensor for use in applications where the closed conduit 31 may sometimes flow only partially full. Absent the inclusion of a depth measurement, this embodiment is primarily applicable to closed pipe flow where the conduit is assumed to be flowing full.
Various embodiments of this invention may be constructed using various types of sensors. Liquid depth may be measured using a pressure transducer, overhead ultrasonic sensor, float, or optical imaging device. Object displacement may be measured using sonic, infrasonic or electromagnetic energy. The sensors may be located within the conduit or they may be externally mounted, as with clamp-on ultrasonic transducers. Having described several preferred embodiments of the invention, various other embodiments, modifications and improvements will be apparent to those skilled in the art, and the invention should be construed as limited only by the spirit and scope of the appended claims.
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The flowmeter of this invention computes the volumetric flow rate of a liquid by measuring the changing positions of objects carried in the flow. This information can be combined with data describing the size, shape and fraction of filling of the conduit. By measuring displacement instead of velocity, accurate measurements of liquid movement can be obtained even when flows are moving very slowly, or not at all.
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RELATED APPLICATION
This application is a divisional of U.S. patent application Ser. No. 09/711,788 filed Nov. 13, 2000, now U.S. Pat. No. 6,544,939.
FIELD OF THE INVENTION
The present invention relates to a silicone dissolving agent and, more particularly, to a silicone dissolving agent that is thickened to remain in contact with a target silicone film.
BACKGROUND OF THE INVENTION
Silicone rubbers are used extensively in electronic, construction, and automotive applications. Silicone rubbers have the attributes of solvent and high temperature resistance, and good adhesion properties to a variety of substrates. Silicone resins and rubbers upon curing are cross-linked polymers. Whereas silicone resins often find applications as electrical insulators and water repellant paints and finishes due to exceptional resistance to weather, sunlight, oxidation and high energy radiation, silicone rubbers, such as RTV silicones, most often find applications as seals and gaskets exposed to temperature extremes and limited classes of olefinic solvents.
Single component silicone rubber mixtures commonly used have good shelf lives and vulcanize at room temperature to yield elastomers. These mixtures generally include a polymeric, usually linear siloxane, a cross linker, a plasticizer such as methyl terminated polydimethyl siloxane and optional additives such as curing accelerators, pigments, processing aids and fillers.
Silicone rubbers and resins are labor intensive to remove and replace. Chemical silicone removers have achieved considerable popularity over abrasive methods such as sandpaper abrasive disks, since abrasion modifies substrate dimensions and finish. Additionally, abrasive grit residue often enters fluid circulatory systems and engine components where the silicone served as a sealant or gasket. Chemical silicone removers have generally been strongly acidic or caustic solutions that are not only able to digest cured silicone rubbers and resins, but also attack metallic substrates such as aluminum and steel. Extreme pH silicone removers have a deleterious effect of pitting metallic substrates and damaging wood substrates as well. Solvent swelling using organic solvents such as alkanols, toluene, methylene chloride and the like are capable of swelling a cured silicone rubber or resin yet still require mechanical abrading or scraping to remove the still cured silicone. Further, environmental concerns and the difficulty of maintaining volatile organic compounds in contact with silicone rubber have limited the utility of this method as well.
Silicone removers have become available based upon organosulfonic acid solutions. While organosulfonic acid solutions are effective in digesting cured silicone rubbers and resins, the high volatility and inability to spread thick layers of such a solution onto a silicone rubber or resin have limited the utility of these solutions in automotive and construction applications. Attempts to formulate a viscous silicone rubber or resin remover by mixing a sulfonic acid compound with a polymeric glycol diether and inorganic particulate as exemplified by Japanese published application 2000061390A have met with limited success owing to incomplete silicone matrix dissolution. Thus, there exists a need for a thickened silicone remover that can be applied to various silicone coated surfaces and remain in contact with the silicone until digested, the thickened silicone remover functioning without degrading the underlying substrate.
SUMMARY OF THE INVENTION
A silicone dissolving composition includes a sulfonic acid compound, a solvent miscible with the sulfonic acid compound, an organic or organometallic material thickener and sulfuric acid. The solvent is selected to swell a silicone matrix. A silicone dissolving composition is also disclosed including alone or in combination sulfonic acid and phosphinic acid, a solvent miscible with the organo-acid, and a thickener present in a concentration sufficient to maintain the composition in dripless contact with a silicone coated substrate until the silicone is dissolved. The solvent chosen is not only miscible with the organo-acid but also is able to swell the silicone matrix. A silicone film is removed by applying a composition according to the present invention to a substrate coated with a silicone film and allowing sufficient time for the silicone film to be dissolved by the composition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The silicone rubber or resin dissolving agent of the present invention includes as an active ingredient from about 0.5 to 25 weight percent of an organo-acid compound, 25 to about 95 weight percent of a solvent miscible with the organo-acid compound and able to swell a cured silicone rubber or resin, a thickener present from about 2 to about 20 weight percent, and an amount of mineral acid present from about 0.025 to about 6% by weight total composition. Preferably, a silicone dissolving agent according to the present invention operates in less than two hours, and more preferably within 2-10 minutes, to digest a silicone to a consistency capable of being wiped from a substrate. Organo-acids according to the present invention include sulfonic acids, phosphinic acids, and phosphonic acids.
“Silicone” is defined herein to include polymeric silicone rubber or resin compositions which are cured or cross linked to form a polymeric matrix.
A sulfonic acid compound according to the present invention has the general formula R 1 SO 3 H where R 1 is an aromatic group, or a C 1 -C 24 alkyl or alkenyl or alkoxy group. Di- or tri-functional sulfonic acids are appreciated to be similarly operative herein. The aromatic group illustratively including phenyl, naphthyl, anthrocenyl, naphthylcenyl, penthacenyl, pyrenyl, phenanthronyl, heterocycles illustratively including pyrimidine, quinoline, isoquinoline, indole, imidazole, purine, furane, and thiophene. Preferably, the aromatic substituent is phenyl. Substituted aromatics operative in the present invention include replacement of an aromatic substituent proton with a group including C 1 -C 20 aliphatics, alcohols, aldehydes, ketones, amines, imides and other heteroatom containing alkyl groups compatible with a hydrosulfonate. Preferably, a substituted aromatic sulfonic acid is a mono or dialkyl substituted phenyl such as dodecyl benzene sulfonic acid. A C 1 -C 20 aliphatic substituent according to the present invention illustratively includes linear, branched, cyclic alkyls and alkenyls. It is appreciated that the choice of R substituent of a sulfonic acid according to the present invention is dictated by factors illustratively including solvent miscibility, silicone matrix interaction, storage stability, commercial availability, viscosity, and handling characteristics.
Optionally, a phosphinic or phosphonic acid having the formula R 2 PO 2 H 2 or R 2 PO 3 H 2 , respectively, is utilized in the present invention in place of, or in combination with, sulfonic acid. R 2 is a radical of coterminus scope with R 1 as detailed with respect to sulfonic acid. Phenylphosphinic acid and phenylphosphonic acids are preferred phosphorus containing acids that are operative herein at levels as low as one weight percent.
A solvent miscible with a given organo-acid is chosen which is capable of swelling a cured or cross-linked silicone. Solvents according to the present invention include aliphatic and aromatic hydrocarbons that are liquid under normal storage and use conditions, illustratively including alkanes, aromatics, ketones, aldehydes, ethers, alcohols and esters. Preferably, a solvent according to the present invention has a limited odor and an evaporation rate less than about half that of n-butyl acetate at 20° C. Owing to the gelled nature of the inventive compositions and rapid silicone dissolution, solvent volatility is of less concern than in prior art compositions. Solvents according to the present invention illustratively include petroleum distillate, hexanes, C 1 -C 8 alcohols and toluene.
A thickener compatible with the silicone remover solvent is provided to promote adherence of a remover according to the present invention with a silicone coated substrate. Thickeners operative in the present invention illustratively include copolymers compatible in the remover solvent, dendrimers, emulsifiers, waxes, resins, inorganics and mixtures thereof.
In addition to the organo-acid utilized herein to dissolve a silicone, it is recognized that trace quantities of sulfuric acid or phosphoric acid typically present in commercial grades of sulfonic acid, and phosphinic and phosphonic acids, respectively, are active in the silicone dissolution process. Sulfuric acid is typically found in commercial grades of sulfonic acid in concentrations ranging from about 0.5 weight percent to about 2 weight percent. While this amount of sulfuric acid is often sufficient to facilitate silicone digestion within a matter of minutes, it is appreciated that sulfuric acid is optionally added beyond this level to modify silicone dissolving agent properties according to the present invention. Preferably, sulfuric acid is added to less than a concentration at which visible substrate pitting or other forms of degradation occurs in metallic substrates such as aluminum and stainless steel. Preferably, sulfuric acid is present at less than 3 total composition weight percent. Similarly, phosphoric acid which is present in phosphinic and phosphonic acids is maintained at levels of less than 3 total composition weight percent.
Optionally, dyes, fillers, wetting agents, defoamers, fragrances and other additives are included in the formulations of the present invention.
The present invention is further detailed with reference to the following illustrative examples. These examples are intended to illustrate various aspects of the present invention and are not intended to limit the scope of the appended claims.
EXAMPLE 1
A sealable mixing chamber was charged with 150 grams of gelled Conosol C-145 (Penreco, Karns City, Pa.). Gelled Conosol C-145 is a thickened aliphatic solvent including approximately 90% hydrotreated light distillate (CAS No. 64742-47-8), about 10% of an aliphatic-aromatic block copolymer thickener and about <0.1% butylated hydroxy toluene. 24 grams of technical grade dodecyl benzene sulfonic acid (DDBSA) of which about 1 gram is sulfuric acid is added to the mixing vessel in conjunction with 90 grams of petroleum distillate (CAS No. 64742-48-9). After mechanical mixing for 30 minutes, a uniform mixture was obtained. The resulting formulation after application readily removed a 4 mil thick blue RTV silicone film from an aluminum substrate within 3 minutes. After storage of the composition for 4 weeks at 50° C., comparable silicone digestion was noted within 3 minutes contact time.
EXAMPLES 2-10
The following total weight percentages were prepared and tested as to removal of 4 mil thick silicone from aluminum substrates. The compositions all wetted a wiping cloth blue after a 3 minute composition contact time with the blue RTV silicone gasket.
TABLE 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
Example 9
Example 10
Gelled Conosol C-145 (wt %)
55.4
56.6
56.5
56.0
55.2
55.0
44.1
57.0
57.0
DDBSA (wt %)
20.1
9.1
8.9
8.9
20.0
20.0
16.1
9.0
1.5
Odorless mineral spirits (wt %)
24.5
34.0
33.8
33.5
24.4
24.2
38.5
0
0
Added sulfuric acid (wt %)
0
0.4
0.8
1.6
0.4
0.8
1.3
0*
0*
Hexanes
0
0
0
0
0
0
0
34.0
41.5*
Total wt %
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
3 min. removal
—
good
good
good
—
—
—
good
4 weeks 50° C.
good
good
good
—
good
good
good
good
3 min. removal
The dodecyl benzene sulfonic acid utilized in Examples 1-10 is a technical grade material containing <2% weight as sulfuric acid.
A range of formulations for the ingredients of Examples 1-10 yielding operative thickened silicone rubber formulations are summarized below in Table 2:
TABLE 2
Total Weight Percent
Gelled Conosol C-145
30-65
DDBSA
1-25
Solvent
20-50
H 2 SO 4
0.025-3
EXAMPLE 11
The composition of Example 1 was reformulated to include 2.6 grams of technical grade p-toluene sulfonic acid in place of DDBSA, 55 grams of toluene and 55 grams of isopropanol as co-solvents in place of petroleum distillate. The resulting composition completely dissolved a 2 mil blue RTV gasket from a stainless steel panel in under 5 minutes without visible damage to the panel.
EXAMPLES 12 and 13
The composition of Example 12 was reformulated with 2.6 grams of technical grade phenylphosphinic acid (Example 12) and 2.6 grams of technical grade phenylphosphonic acid (Example 13) with similar successful silicone gasket removal.
EXAMPLE 14
As a comparative example, compositions utilizing polymeric glycol ethers and sulfonic acid as a dissolving agent for cured silicone rubber was evaluated. Dowanol EB glycol ether (Dow Chemical Company, Midland, Mich.) was utilized as a polymeric glycol ether source. Comparative Examples 1 and 2 are compared with a formulation corresponding to that of Example 1 are shown in Table 3 along performance results for these various formulations.
TABLE 3
Weight Percent
Comparative
Comparative
Example A
Example B
Example 1
Dowanol EB Glycol
34.0
91.0
0
Ether
Biosoft S-100
9.0
9.0
9.0
(DDBSA*)
Gelled Conosol C-145
57.0
0
57.0
Odorless Mineral Spirits
0
0
34.0
Formula appearance:
two distinct phases,
thin, pale amber
thick, smooth
components not
liquid
amber gel
miscible
Removal time:
not applicable due
˜14 hours
5 minutes
Film appearance at
to phase separation
bubbled & peeling
completely
removal:
dissolved
*Dodecyl benzene sulfonic acid
EXAMPLE 15
The formulation of Example 4 was reproduced with the substitution of para-toluene sulfonic acid for dodecyl benzene sulfonic acid with comparable results being obtained.
Patents and patent applications referenced herein are intended to be incorporated by reference to the full extent as if each individual patent or patent application was individually and specifically incorporated herein by reference.
It is to be understood that the preceding example are illustrative of the present invention. One skilled in the art will readily appreciate various modifications of the present invention without departing from the spirit thereof. These modifications are intended to fall within the scope of the appended claims.
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A silicone dissolving composition includes an organo-acid compound such as sulfonic acid or phosphinic acid, a solvent miscible with the organo-acid and able to swell a silicone, a thickener and a small amount of mineral acid. Silicone films dissolve to a liquefied mass capable of being wiped from a substrate in a matter of minutes. The removal of automotive, electrical, and construction sealants and gaskets is simplified with the use of such a silicone dissolving composition.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of application Ser. No. 11/385,545, filed Mar. 21, 2006, now U.S. Pat. No. 8,046,506, the entirety of which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to FIFO devices, and in particular, to a FIFO sharing mechanism for data reproduction.
2. Description of the Related Art
FIG. 1 shows a conventional FIFO system 100 coupled to a first device 115 and a second device 125 . The FIFO system 100 comprises a memory controller 120 , a CPU 130 , a first FIFO device 140 and a second FIFO device 150 . The memory controller 120 is controlled by the CPU 130 to access a memory device 110 . The first FIFO device 140 serves as an interface for instruction transfer to and from the first device 115 , and the second FIFO device 150 for second device 125 . The instructions transferred via the first FIFO device 140 and second FIFO device 150 , comprise two types, status and data. Status instructions delivered from the first device 115 or second device 125 are parsed and executed by the CPU 130 , and data instructions from the first device 115 and second device 125 are sent to the memory device by the memory controller 120 . Thus, each of the devices 115 and 125 is simultaneously coupled to the memory controller 120 and CPU 130 , with a detection mechanism required determining instruction types stored therein, such that the instructions can be directed accordingly.
FIG. 2 a is a flowchart of a conventional data reading process. In step 202 , when the FIFO system 100 requests data from first device 115 , the CPU 130 initializes the transfer by sending a status instruction to the first FIFO device 140 . The first device 115 then reads the status instruction from the first FIFO device 140 , and performs an initialization to determine whether the requested data is available. In step 204 , a status instruction is delivered from the first device 115 to the first FIFO device 140 , indicating the availability of the requested data. Thereafter, the CPU 130 reads the status instruction in the first FIFO device 140 . In step 206 , if the requested data is available, the first device 115 delivers at least one data instruction carrying the requested data to the first FIFO device 140 . Upon confirmation of the availability of the requested data according to the returned status instruction, the CPU 130 commands the memory controller 120 to read the data instruction from the first FIFO device 140 and sends it to the memory device.
FIG. 2 b is a flowchart of a conventional data writing process. In step 212 , when the FIFO system 100 requests to write data from the memory device to the second device 125 , the CPU 130 initializes the transfer by sending a status instruction to the second FIFO device 150 . The second device 125 then reads the status instruction from the second FIFO device 150 , and performs an initialization to determine whether the second device 125 is capable of storing the data. In step 214 , in response, a status instruction is delivered from the second device 125 to the second FIFO device 150 , indicating the capability for storage. The CPU 130 reads the returned status instruction in the second FIFO device 150 to confirm the capability. In step 216 , upon confirmation of the capability for data storage according to the returned status instruction, the CPU 130 commands the memory controller 120 to deliver the data instruction from the memory device to the second FIFO device 150 . In step 218 , when the second device 125 obtains the data instruction through the second FIFO device 150 , it responds another status instruction as an acknowledgement. Through the second FIFO device 150 , the CPU 130 reads the acknowledgement to conclude the data transfer.
The FIFO system 100 may be a card reader, whereas the first device 115 and second device 125 are memory cards such as SD or CF cards. When there is need to copy data from the first device 115 to the second device 125 , or vice versa, the processes shown in FIGS. 2 a and 2 b are performed. The memory device and CPU 130 occupy significant system resources and time. Additionally, the determination of instruction type also consumes considerable computation power of the CPU 130 . A more efficient architecture is thus desirable.
BRIEF SUMMARY OF THE INVENTION
A detailed description is given in the following embodiments with reference to the accompanying drawings.
A FIFO system is provided, transferring data between a first device and a second device, in which a memory controller serves as an interface to access a memory device for storage of the data, and CPU processes instructions to control the data transfer. The FIFO system may also comprise a first data FIFO serving as a data buffer for data transactions to and from the first device, a first status FIFO coupled to the first device and the CPU serving as an instruction buffer for status transactions between the first device and the CPU, a second data FIFO serving as a data buffer for data transactions to and from the second device, and a second status FIFO coupled to the second device and the CPU serving as an instruction buffer for status transactions between the second device and the CPU. A FIFO controller connects the first data FIFO and second data FIFO for direct data delivery therebetween.
In another embodiment, the two data FIFOs are merged to one, serving as a shared data buffer for data transactions to and from the first and second devices. A FIFO controller is further provided, coupled to the first status FIFO, second status FIFO and data FIFO, multiplexing data and status transactions to and from the first and second devices.
In a further embodiment, the two status FIFOs are also merged to one, serving as a shared instruction buffer for status transactions between the first device, second device and the CPU. Thus a FIFO controller is provided, coupled to the data FIFO and the status FIFO, multiplexing data and status transactions to and from the first and second devices.
The said first and second devices can be the same type or different type. The device type can be MS card, SD card, CF card, or any other device conforming IEEE 1394 or USB standards.
Embodiments of FIFO operating method implemented on the FIFO systems described are also provided.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
FIG. 1 shows a conventional FIFO system 100 coupled to a first device 115 and a second device 125 ;
FIG. 2 a is a flowchart of a conventional data reading process;
FIG. 2 b is a flowchart of a conventional data writing process;
FIG. 3 a shows an embodiment of a FIFO system 300 coupled to the first device 115 and second device 125 ;
FIG. 3 b shows an embodiment of a FIFO controller 330 in the FIFO system 300 according to FIG. 3 a;
FIG. 3 c is a flowchart showing an embodiment of a data reproduction process according to the architecture in FIG. 3 a;
FIG. 4 a shows an embodiment of a FIFO system 400 coupled to the first device 115 and second device 125 ;
FIG. 4 b shows an embodiment of the FIFO controller 450 in the FIFO system 400 according to FIG. 4 a;
FIG. 4 c is a flowchart showing an embodiment of a data reproduction process according to the architecture in FIG. 4 a;
FIG. 5 a shows an embodiment of a FIFO system 500 coupled to the first device 115 and second device 125 ; and
FIG. 5 b shows an embodiment of the FIFO controller 550 in the FIFO system 500 according to FIG. 5 a.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 3 a shows an embodiment of a FIFO system 300 coupled to the first device 115 and second device 125 . The FIFO system 300 comprises a FIFO controller 330 , a CPU 130 , a first data FIFO 310 , a first status FIFO 315 , a second data FIFO 320 , and a second status FIFO 325 . The first data FIFO 310 and the first status FIFO 315 are interfaces for the first device 115 , individually passing status and data instructions respectively, and the second data FIFO 320 and the second status FIFO 325 are for the second device 125 . The two sets of interfaces are identical, so only that of the first device 115 is used for description. For example, instructions sent from the first device 115 , are categorized in the arbitrator 314 according to instruction type, thus data instructions are sent to the first data FIFO 310 , and status instructions to the first status FIFO 315 . The FIFOs may be bidirectional, whereas instructions bound to the first device 115 are also provided to the first data FIFO 310 and first status FIFO 315 , and the first device 115 reads them thereafter via the arbitrator 314 . The arbitrator 314 is coupled to the first data FIFO 310 and first status FIFO 315 , respectively diverting the data and status instructions from the first device 115 to the first data FIFO 310 and first status FIFO 315 , and conversely from the first data FIFO 310 and first status FIFO 315 to the first device 115 . The arbitrator 324 serves the same function for the second data FIFO 320 , second status FIFO 325 and second device 125 . Since the Status instructions are typically machine codes executing specific functions, handled by the CPU 130 , no status interaction is required between the first device 115 and second device 125 . With the CPU 130 , status instructions are delivered to and from the first device 115 via the first status FIFO 315 , and the second device 125 via the second status FIFO 325 . In the FIFO controller 330 , a data controller 350 is provided to dominate data instruction flow. Specifically, the data controller 350 handles data instruction delivery between any two of the first data FIFO 310 , second data FIFO 320 and memory controller 120 . The FIFO controller 330 also comprises a memory controller 120 controlled by the CPU 130 to handle memory access of the memory device 110 .
FIG. 3 b shows an embodiment of the FIFO controller 330 in the FIFO system 300 according to FIG. 3 a . The data controller 350 comprises a first selector 312 and a second selector 322 . The first selector 312 is coupled to outputs of the second data FIFO 320 and memory controller 120 , selecting one thereof as an input to the first data FIFO 310 . Identically, the second selector 322 coupled to outputs of the first data FIFO 310 and memory controller 120 selects one thereof as an input to the first data FIFO 310 .
FIG. 3 c is a flowchart showing an embodiment of a data reproduction process according to the architecture in FIG. 3 a . When data is to be copied from the first device 115 to the second device 125 , the data controller 350 provides a direct data path that does not occupy the memory controller 120 or memory device 110 . In step 301 , When the FIFO system 300 performs a copy operation to copy data from the first device 115 to the second device 125 , the CPU 130 sends status instructions #St 1 and #St 2 to the first device 115 and second device 125 via the corresponding first status FIFO 315 , arbitrator 314 , second status FIFO 325 and arbitrator 324 to initialize the copy operation. The status instructions are of status type according to IEEE 1394 standard. For example, the CPU 130 initializes a read operation on the first device 115 by SET_RW_REG_ADRS, WRITE_REG and SET_CMD instructions. Simultaneously, the CPU 130 also initializes a write operation on the second device 125 by CMD 0 , ACMD 41 , CMD 2 , CMD 3 and CMD 7 instructions. In step 302 , the first device 115 and second device 125 respond with corresponding status instructions #St 1 and #St 2 to the CPU 130 via the corresponding arbitrator 314 , first status FIFO 315 , arbitrator 324 and second status FIFO 325 as an acknowledgement. In step 303 , when the acknowledgement is confirmed by the CPU 130 , the data requested for copy is transferred. The first device 115 writes the data to the first data FIFO 310 via the arbitrator 314 , and the data controller 350 copies the data from the first data FIFO 310 to the second data FIFO 320 as indicated in arrow #D 1 . The second device 125 then reads the data in the second data FIFO 320 via the arbitrator 324 , as indicated in arrow #D 2 .
FIG. 4 a shows an embodiment of a FIFO system 400 coupled to the first device 115 and second device 125 . In the FIFO system 400 , a first status FIFO 410 serves as an instruction buffer for status transactions #St 1 between the first device 115 and the CPU 130 , and a second status FIFO 420 serves #St 2 between the second device 125 and the CPU 130 . A data FIFO 430 is provided as a shared data buffer for data transactions #D for the memory controller 120 , first device 115 and second device 125 . Since the first device 115 and second device 125 read and write data by control of the status instructions, the data instructions can be commonly stored in the data FIFO 430 without confusion. A FIFO controller 450 is coupled to the first status FIFO 410 , second status FIFO 420 and data FIFO 430 , multiplexing transactions to and from the first device 115 and second device 125 . The FIFO system 400 provides backward compatibility for the first and second devices 115 and 125 , because the instructions transactions #C 1 and #C 2 still follow conventional protocol.
FIG. 4 b shows an embodiment of the FIFO controller 450 in the FIFO system 400 according to FIG. 4 a . The FIFO controller 450 comprises three selectors and two arbitrators, switching for the data flow, in which a first selector 412 is coupled to the first status FIFO 410 and the data FIFO 430 , forwarding output therefrom to the first device 115 as Cin 1 . A second selector 422 is coupled to the second status FIFO 420 and the data FIFO 430 , forwarding output therefrom to the second device 125 as Cin 2 . A third selector 432 is coupled to the data FIFO 430 , forwarding data delivered from the first device 115 and second device 125 bound for the data FIFO 430 as Din. The FIFO controller 450 transparently provides individual data paths from the first status FIFO 410 , second status FIFO 420 and data FIFO 430 to the first device 115 and second device 125 operating conventionally, such that no compatibility issues occur. Further in the FIFO controller 450 , a first arbitrator 414 is coupled to the third selector 432 and the first status FIFO 410 , diverting status instructions from the first device 115 to the first status FIFO 410 , and data instructions from the first device 115 to the third selector 432 . A second arbitrator 424 is coupled to the third selector 432 and the second status FIFO 420 , serving the same for the second device 125 .
FIG. 4 c is a flowchart showing an embodiment of a data reproduction process according to the architecture in FIG. 4 a . In step 401 , when the FIFO system 400 performs a copy operation to copy data from the first device 115 to the second device 125 , the CPU 130 sends status instructions to the first device 115 and second device 125 via the corresponding first status FIFO 410 and second status FIFO 420 to initialize the copy operation. In step 402 , the first device 115 and second device 125 respond with corresponding status instructions to the CPU 130 via the first arbitrator 414 , second arbitrator 424 , first status FIFO 410 and second status FIFO 420 as an acknowledgement. In step 403 , when the acknowledgement is confirmed by the CPU 130 , the first device 115 writes data to the data FIFO 430 via the first arbitrator 414 and third selector 432 . Thereafter, the second device 125 reads the data in the data FIFO 430 via the second selector 422 .
FIG. 5 a shows an embodiment of a FIFO system 500 coupled to the first device 115 and second device 125 . In this embodiment, a data FIFO 502 and a status FIFO 504 are provided. The data FIFO 502 serves as a shared data buffer for all data transactions #D between all devices and the memory controller 120 . The status FIFO 504 coupled to the CPU 130 , serves as a shared instruction buffer for all status transactions #St between all devices and the CPU 130 . To maintain transparency and compatibility for the first device 115 and second device 125 , a FIFO controller 550 is provided. The FIFO controller 550 is coupled to the data FIFO 502 and the status FIFO 504 , multiplexing data and status transactions #C 1 and #C 2 to and from the first device 115 and the second device 125 .
FIG. 5 b shows an embodiment of the FIFO controller 550 in the FIFO system 500 according to FIG. 5 a . The FIFO controller 550 comprises two arbitrators and two selectors. A first arbitrator 512 is coupled to the data FIFO 502 , diverting data output Cout 1 and Cout 2 from the first device 115 and second device 125 to the data FIFO 502 . A first selector 514 is coupled to the data FIFO 502 and status FIFO 504 , forwarding output Dout and Sout therefrom to the first device 115 . A second arbitrator 522 is coupled to the status FIFO 504 , diverting status instructions output from the first device 115 and second device 125 to the status FIFO status FIFO 504 . The second selector 524 is coupled to the data FIFO 502 and status FIFO 504 , forwarding output Dout and Sout therefrom to the second device 125 . When the FIFO system 500 performs a copy operation to copy data from the first device 115 to the second device 125 , the CPU 130 sends status instructions to the first device 115 and the second device 125 via the status FIFO 504 , first selector 514 and second selector 524 to initialize the copy operation. The first device 115 and second device 125 respond with corresponding status instructions to the CPU 130 via the second arbitrator 522 and status FIFO 504 as an acknowledgement. When the acknowledgement is further confirmed by the CPU 130 , the first device 115 writes data to the data FIFO 502 via the first arbitrator 512 . Thereafter, the second device 125 reads the data in the data FIFO 502 via the second selector 524 . In the embodiment, one data FIFO 502 is shared by all devices, such that implementation of a plurality of data FIFOs for each device is not required, and costs are reduced significantly.
In the disclosed embodiments, the first device 115 and second device 125 are individually a MS card, a SD card, a CF card, or a device conforming IEEE 1394 or USB standards. The FIFO systems described are not limited to serving only two devices at once. On the contrary, a plurality of devices may be coupled together based on the described architecture in FIGS. 3 a , 4 a and 5 a . When a FIFO device is shared by multiple devices, an extra flag is provided to indicate which device a data or status instruction belongs to. The selectors and arbitrators may be specifically designed circuits self-triggered upon reception of a corresponding instruction. The selectors are multiplexing circuits capable of selecting one of two inputs as an output, and the arbitrators are capable of distinguishing instruction types and diverting them accordingly. Alternatively, the selectors and arbitrators may be function blocks implemented by software for control of data flowing in and out the FIFO system.
While the invention has been described by way of example and in terms of preferred embodiment, it is to be understood that the invention is not limited thereto. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.
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FIFO systems and operating method thereof are provided to transfer data between a first device and a second device. In the FIFO system, a memory controller serves as an interface to access a memory device for storage of the data, and a CPU processes instructions to control the data transfer. Two data FIFOs serve as data buffers for data transactions to and from the first and second devices, and two status FIFOs serve as an instruction buffers for status transactions between the first, second devices and the CPU. A data controller connects the memory controller and the two data FIFOs for direct data delivery therebetween.
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FIELD OF THE INVENTION
[0001] This invention has to do with dispenser pumps for dispensing discrete doses of a flowable material from a container on which the pump is fitted. The present proposals have particular relevance to dispenser pumps for use with viscous or pasty materials. They are also relevant when material to be dispensed needs to be protected from contact with air e.g. to prevent drying out or degradation. We particularly envisage that the invention may be embodied in a toothpaste dispenser.
BACKGROUND
[0002] In recent years toothpaste dispensers have become widely available in which a relatively large volume of paste is contained in a free standing container, and a piston-and-cylinder dispenser pump with a fixed discharge nozzle is provided at the top of the container to dispense a dose of toothpaste when the pump piston is depressed. Known pumps include arrangements for covering, blocking or shielding the discharge nozzle outlet between operations of the pump to keep the residual paste in the pump from drying out and to help separate the tail end of each dispensed dose from the nozzle tip. Toothpaste is extremely sticky and there are often problems in that slugs of paste issuing forth are not cleanly cut off, leading to toothpaste being smeared over the outside of the nozzle tip by the cover arrangement which is precisely the opposite of what is wanted.
THE INVENTION
[0003] The aim here is to propose new and useful dispenser pumps including a novel arrangement for blocking a discharge nozzle of the pump. A particular aim is to provide a pump which is for use with materials of the kinds mentioned above e.g. toothpaste.
[0004] In general terms, a dispenser pump of the relevant kind has a pump chamber whose volume is alterable in a pumping stroke by relative movement between a body of the pump and a plunger which is reciprocable relative to the body by hand actuation. Typically the plunger has a piston which works in a cylinder of the pump body, the piston and cylinder defining a pump chamber between them. An inlet is provided for flowable material to enter the pump chamber from a container to which the pump is secured, and an outlet of the pump chamber leads to a discharge passage which extends along a discharge nozzle to an external nozzle opening. Usually a one-way inlet valve is necessary and a one-way discharge valve is preferred.
[0005] A blocking element is provided, dimensioned to close off the discharge passage and arranged for guided movement transverse to the discharge passage between blocked and open positions. Preferably the blocking element traverses the discharge passage at a blocking location which is at or adjacent the external nozzle opening. The discharge nozzle construction includes a guide track leading around a bend to the blocking location. Preferably this bend or angle is substantially in longitudinal register with the blocking location. An elongate drive connector extends along this guide track, and is longitudinally slidable relative to it. This connector has a proximal part connected to the pump plunger, so that operation of the pump by moving the plunger relative to the pump body drives longitudinal movement of the drive connector along the guide track. A distal portion of the drive connector acts on the blocking element, preferably by being joined to or integral with it. The drive connector is also flexible, so as to be able to negotiate the bend in the guide track. By these means, operation of the pump by moving the plunger relative to the body drives movement of the blocking element across the discharge passage between the blocked and open positions.
[0006] By having the distal part of the drive connector joined to or integral with the blocking element, it can both push and pull the blocking element. Correspondingly, it is preferred that the proximal part of the drive connector is connected to the pump plunger in such a way that the two directions of plunger movement positively drive respectively the opening and closing of the discharge passage. The drive connector may include one or more non-flexing parts which do not pass around a bend and are thickened or reinforced relative to the flexing part(s), helping to avoid buckling under longitudinal compression.
[0007] The guide track preferably has a portion which extends alongside the discharge passage, leading around a distal bend to a transverse portion adjacent the blocking location. Guide track engagement at the outside of the bend, preferably by one or more curved elements, enables transverse action of the blocking element by pushing. Guide track engagement on the inside of the bend enables transverse action of the blocking element by pulling. Preferably both are present.
[0008] In preferred pumps the discharge nozzle extends generally transversely to the direction of the plunger action. In this situation the guide track may have a proximal corner which is between a longitudinal portion extending along the discharge nozzle and a proximal portion extending in the plunger's direction of action. Again, guide track engagements to the inside and outside of such a corner enable pulling and pushing actions of the connector respectively and are preferably combined.
[0009] By these means, plunger movement in one direction may drive movement of the blocking element relative to the transversally-extending discharge passage in substantially the opposite direction.
[0010] Even when the discharge nozzle and plunger action are mutually transverse, it is possible to avoid the need for the drive connector to flex around more than one corner. This may be desirable because it reduces the longitudinal extent of the connector required to be flexible, and therefore reduces any tendency for it to buckle under compression. A way of achieving this is by having a coupling between the plunger action and the drive connector proximal end which is pivoted around an axis perpendicular to the plunger axis and to the guide track, the coupling and the proximal end of the drive connector being joined (preferably flexibly) at a joint substantially at a tangent point of the drive connector with respect to the coupling's pivot axis. Such a coupling may for example be comprised in a pivoted actuating lever for the dispenser pump which acts on both the pump plunger stem and the drive connector for the blocking element.
[0011] A preferred disposition of the pump for these purposes, as indeed for the others, has the pump arranged with its plunger axis generally upright at the back of the dispenser, the discharge passage extending from the outlet at the bottom of the pump, up in front of the pump and then forwardly along the discharge nozzle to the discharge opening. The discharge nozzle is preferably at substantially the same height at the actuating portion at the top of the pump plunger.
[0012] A preferred form of the flexible elongate drive connector is a strip or tongue form, since this flexes more readily in one sense than in the perpendicular sense, facilitating guiding. It is generally convenient to arrange all guide track bends to be in one plane. A strip-form connector is also easy to form in plastics material. It may be formed as an integral projection on one of the pump components e.g. a plunger part. Furthermore the blocking element may itself be an integral continuation of the drive connector, e.g. an end thereof.
[0013] A blocking element which is a continuation of a flexible connector strip may itself pass around a corner of the guide track adjacent the blocking location, reducing the transverse dimension required for the nozzle. The blocking element may therefore also be flexible.
[0014] For a strip-form connector the guide track is preferably an elongate slot. A suitable track may be formed between complementarily-shaped opposed surfaces of two discharge nozzle components.
[0015] Means may be provided for reducing friction along the guide track. One or both components, preferably at least the connector, may be made from low-friction material or provided with a friction-reducing coating. A guide track for a strip-form connector can have one or more localised surface projections e.g. ribs to engage the connector with reduced contact area.
[0016] A preferred refinement of the pump assures at least partial opening of the discharge passage before the pump pressurizes the material in it. This is achievable by connecting the drive connector to an actuating part of the pump plunger such as a button or lever, and providing some lost motion in the connection between the actuating part and a piston part, so that driving of the piston begins only after some movement of the blocking element away from the blocked position.
[0017] As suggested above, a preferred embodiment of the invention is a toothpaste dispenser in which the dispenser is mounted at the top of a container for toothpaste adapted for airless dispensing e.g. by a container base in the form of a follower piston which rises up the container as material is dispensed, or by means of a flexible container or flexible container liner which gradually collapses as material is dispensed.
[0018] Combining various preferred features disclosed above, a preferred dispenser pump of such a toothpaste dispenser is as follows. The fixed pump body incorporates a fixed discharge nozzle projecting laterally. The pump plunger carries a piston operable in a cylinder of the pump body, with the plunger axis generally upright. The pump chamber inlet is into the bottom of the cylinder through a pump body base spanning the top of the container. The pump chamber outlet opens downwardly from the pump chamber e.g. into a annular discharge space leading to an initial riser portion of the discharge passage alongside the pump cylinder and them round an angle into a transverse portion of the discharge passage in the projecting discharge nozzle. The discharge nozzle includes inner and outer nozzle parts which fit together to define between them a guide track extending along the discharge nozzle and round a distal bend adjacent its end to open transversely onto the discharge passage adjacent its exterior opening.
[0019] In one version the inner end of the guide track bends inwardly and down around the angle between the first and second parts of the discharge passage, and accesses the side of the moveable plunger. A flexible strip is attached to the side of the plunger—e.g. formed integrally with it—and extends along the guide track up around the inside bend, along the nozzle and down out of the guide track's distal opening to act across the discharge passage.
[0020] In another version a pivoted coupling is provided, connected to both the flexible strip and the pump plunger so that no inside bend of the strip is required.
[0021] The end of the strip fully blocks the discharge passage in the raised position of the plunger; its end edge may then seat in a recess on an opposing lower side of the discharge passage. Depression of the plunger pulls the strip along the guide track, flexing as it passes round the bend(s) and drawing the end blocking portion up out of the discharge passage and at least partially into the distal bend of the guide track. On release the plunger rises under the force of a restoring spring, pushing the flexible strip back along the guide track and its tip back across the discharge passage adjacent the nozzle opening to close it off. The closeness of fit of the strip in the guide track can be selected, along with suitable thickness of the strip, to enable this pushing effect without kinking or crumpling of the strip.
[0022] Embodiments of these proposals are now described by way of example.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] [0023]FIG. 1 is an axial sectional view of a toothpaste dispenser pump, showing also the top of a toothpaste container;
[0024] [0024]FIG. 2 is a view from below and behind of a nozzle outer shell;
[0025] [0025]FIG. 3 is a view from above and behind of a nozzle core component;
[0026] [0026]FIG. 4 is an exploded view showing an operating button, a cylinder component and a piston element;
[0027] [0027]FIG. 5 is a side view of a body top insert;
[0028] [0028]FIG. 6 is a view from above and in front of a main body shell;
[0029] [0029]FIG. 7 is a view from above and one side of a body base, and
[0030] [0030]FIGS. 8 and 9 are axial sectional views of a second embodiment in rest and pressed conditions.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0031] A first embodiment of dispenser pump, designed for dispensing toothpaste, is shown in FIGS. 1 - 7 . In terms of its structural components, the dispenser includes a toothpaste container 8 whose specific construction is of no particular relevance, a pump base 11 spanning the top of the toothpaste container 8 (and shown in FIG. 7), a pump body component 12 fitting onto the pump base 11 (seen in FIG. 6) and a cylinder 16 , seen in the centre of FIG. 4, which is mounted in the pump body 12 . A pump plunger and attached piston 21 , 23 ,also seen in FIG. 4, operate along a generally upright axis in the cylinder 16 . A discharge nozzle at the top front of the pump is provided by a discharge channel component 15 housed beneath a top nozzle shroud 14 (FIG. 2). A top insert 13 (FIG. 5) fits onto the top of the pump body 12 to hold the plunger components in place and guide their stroke.
[0032] Considering these components now in more detail, the pump body 12 includes a cylinder housing 122 with a forwardly-opening axis or tracking slot 124 , and an annular chamber 125 forming a discharge space with an upwardly-directed discharge opening 121 . The cylinder proper 16 fits coaxially into the cylinder housing 122 , being held down in place by an annular flange 161 trapped below the cylinder housing.
[0033] The pump base 11 has an inlet opening 111 in which an inlet valve body, comprising a blocking disc 512 and sliding retaining legs 511 , is fitted. Other kinds of inlet valves may be used if wished. An annular space 61 surrounds the projecting inlet conduit 111 , and an annular elastomeric outlet valve 52 is fitted over this. This outlet valve has a lower cylindrical sleeve which clamps it down onto the inlet conduit 111 , a central hole for the inlet opening, and a flat radial flap projection which bears resiliently against the bottom edge of the cylinder flange 161 .
[0034] The plunger construction includes a plunger cap 21 , a piston 23 and a flexible closure strip or tongue 22 . See FIG. 1 and FIG. 4. The piston 23 has a conventional double-acting flexible seal 232 engaging the wall of the cylinder 16 to define a pump chamber for inside the cylinder, governed by the inlet and outlet valves described above. The stem 234 of the piston is joined to the underside of the plunger cap 21 with some axial lost motion by means of a securing bolt 212 which traps its top end in a tubular formation of the cap 21 . The reduced-diameter top end of the stem is axially slidable to a limited extent in this formation of the cap, so that when the cap is depressed the piston initially does not move until a downwardly-directed shoulder 211 of the cap formation meets an upwardly-directed shoulder 231 of the stem. The reason for this is explained below.
[0035] A conventional steel pump spring 3 is trapped between the plunger cap and ah inward projection of the cylinder 16 so that the plunger is continually urged upwardly relative to the cylinder, and the plunger cap 21 and piston 23 are urged apart.
[0036] At the front of the pump the upward opening 121 of the annular discharge chamber 125 opens into the bottom end of the discharge channel component 15 . This component is essentially a rectangular-section pipe with an upright leg 156 joined via a substantially right-angled bend to a longitudinal leg 157 . It is supported from below by the pump body 12 and held in place from above by the nozzle shroud 14 , which includes a front opening 631 registering with the front opening of the channel 15 .
[0037] The upper and outer surface of the channel 15 complements the undersurface of the nozzle shroud 14 so that a guide track is defined between them. Specifically, longitudinal side flanges 158 of the channel 15 meet corresponding downward ribs of the shroud 14 to act as spacers. Opposed upward and downward central ribs 151 , 141 on these components are then held at a substantially uniform slit spacing as seen in the section of FIG. 1. To either side of these ribs the shroud and channel surfaces are recessed away to reduce friction. Rearwardly of the nozzle shroud 14 the outer spacer ribs 158 and inner guide rib 151 of the channel 15 continue back down around the bend 154 and onto the riser leg 156 . At the bend 154 they are opposed by corresponding spacer and guide formations on the top insert 13 , not shown in detail but apparent from FIG. 1.
[0038] The flexible strip 22 is formed integrally on the front of the plunger cap 21 . It is moulded in one piece with the cap, and takes the form of a blade or tongue of generally uniform width and thickness extending from a root block 225 at the front of the cap 21 . This block 225 fits and is guided in the front track opening 124 of the pump body 12 . The blocking strip 22 has an as-moulded conformation as shown in FIG. 4, generally matching the conformation of the guide track defined around the outer surface of the channel 15 . Thus it has a proximal bend 224 , a longitudinal straight portion 223 , a distal bend 222 and an end portion 221 which also serves as a blocking portion. Alternatively it may be formed straight (i.e. parallel to the cap axis) which requires bending on installation but improves resistance to buckling under compression.
[0039] The strip/plunger cap components are moulded from polypropylene material incorporating anti-static and slip additives which give low frictional resistance to movement of the strip 22 along the guide track. The end, blocking portion 221 of the strip is dimensioned so that as seen in FIG. 1 it can extend right across the front opening of the channel 15 and finish in a guide slot at the opposite, lower side of the shroud opening 631 . Its side edges also engage behind overlapping side guide portions of the shroud 14 adjacent to the opening 631 to guide its movement across the opening.
[0040] The operation of the pump is as follows. Its rest condition is as shown in FIG. 1. The user presses the plunger cap 21 . The initial part of the stroke takes up the lost motion between the cap 21 and the piston stem 234 , so the piston 23 does not move. However the root 225 of the blocking strip 22 starts to move down the slot 124 and starts to pull the strip 22 back along the guide track, with flexion as it passes around the inner and outer bends thereof, and withdrawing the end blocking part 221 of the strip from the nozzle's outer opening 631 . Thus, when the opposed shoulders 211 , 231 of the plunger cap 21 and piston stem 234 meet and the piston starts to move down, forcing toothpaste out from the pump chamber (via the outward valve 52 , the riser of portion 62 of the discharge passage and the nozzle portion 63 of the discharge passage) the opening 631 is already at least partially unobstructed so that there is no undue pressure build-up.
[0041] The plunger stroke continues to the bottom, or as far as the user wishes in terms of the amount of toothpaste wanted, and is then released. The spring pushes the plunger cap 21 up again, carrying the root of the strip 22 up along the track 124 and pushing the strip 22 back along its guide track. The blocking end 221 of the strip—which was previously flexed around the corner above the discharge nozzle—is pushed back into position across the nozzle opening 631 , cutting off the toothpaste cleanly. By having the blocking location closely adjacent to the nozzle opening 631 , exposed residues are minimised. The anti-slip properties of the strip 22 then help prevent toothpaste from sticking. In alternative embodiments it may be arranged that the outer opening 631 of the shroud is substantially wider than the adjacent inner opening of the channel (although still making any necessary guiding engagements with the blocking element) to further reduce the surface available for toothpaste to stick to adjacent the opening after dispensing.
[0042] As the plunger rises the pump chamber is refilled in a conventional manner through the inlet valve.
[0043] The reader will note how the disposition of the bend and its corresponding guide portions 143 , 153 immediately adjacent the nozzle opening can minimise the increase in dimensions of the discharge nozzle caused by having the internal guide track running along it.
[0044] Depending on the specific materials and orientations of the pump components, it may in some cases be found that a rather large force is needed on the return stroke to push the flexible element 22 back around the bends., taking into account sufficient sturdiness of the flexible component to avoid buckling under compression. This means a stronger pump spring which may sometimes be undesirable.
[0045] [0045]FIGS. 8 and 9 show a second embodiment which addresses this issue. Instead of a plunger cap, this embodiment uses an actuating lever 9 pivoted at the front of the dispenser. Here the pivot connection 91 is provided at the front of the discharge channel component 15 . Connection of the actuating lever 9 to the pivot 91 is via a pair of opposed side pieces 92 to either side of the channel 15 , which meet at a bridge connector 94 just above the channel 15 adjacent its rear bend 154 . This bridge connector 94 is at the shortest accessible radius relative to the pivot 91 . The flexible blocking strip 22 is joined at the front of this bridge portion 94 , e.g. integrally by means of a “living hinge” moulded in plastic, and extends along the guide track and round the front bend 153 as in the previous embodiment. An important difference here however is that the proximal portion 229 of the strip 22 is substantially thickened so that it is less liable to buckling when pushed forward along the track. Because this portion does not need to pass around any significant bend of the track, this thickening does not increase the force required. Since it is not liable to buckling, the guide track need engage it only from beneath and this reduces friction. The guide track engages the outside of the flexible strip only at and adjacent the bend next to the front opening (as in the first embodiment). Here the strip 22 is thinner so as to flex readily around the bend.
[0046] Since the actuating lever must move in an arc it cannot be fixed with the piston. Rather, we provide a curved cam boss 95 on its undersurface which engages a flat top surface 236 of the piston stem. The pump is positioned upright to bring the cam engagement position substantially forward of the rear end of the actuating lever 9 and this provides mechanical advantage, i.e. reduced required user force, in operating the pump and in moving the closure tongue 22 .
[0047] While not shown in this embodiment, it could of course be arranged for some lost motion in the coupling of the lever 9 and piston to provide an early opening of the nozzle, as in the first embodiment.
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A dispenser pump e.g. for toothpaste has a plunger ( 21 ) connected to a proximal end of an elongate flexible plastics strip ( 22 ) which is run slidably along a guide track built into the discharge nozzle ( 14 ) of the pump alongside the discharge channel ( 63 ). The distal end of the guide track defines a bend which opens through a lateral slot into the discharge channel ( 63 ) just inside its external opening. Action of the plunger causes the strip ( 22 ) to slide back and forth along the track and round the bend, so that the tip of the strip is moved out of the mouth of the nozzle during dispensing but returns to block it and cut away residual product when the plunger is released.
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BACKGROUND OF THE INVENTION
The invention relates to fastening means for flexible panels, and more particularly to a releasable fastening and holding means for the edges of flexible film layers which form a part of an inflated structure.
Various connecting devices and fasteners for flexible panels and sheets have been suggested.
Commonly-owned U.S. Pat. No. 3,464,480 shows a multiple-component fastener for suspending a flexible panel or sheet in vertical position. This device requires the sheet to have a hem through which a bar is placed which is then locked between two other components of the fastener. In this type of device, the direction of the pull on the sheet will not vary and it is not intended to seal two or more sheet edges together.
U.S. Pat. No. 3,805,873 shows a two-component elongate fastener including a channel having opposed concave sides for receiving a flat locking member. The flexible panel is wrapped around the locking member and as such may be inserted into a deeper of the two concave ends and freely slipped into the other concave end. When tension is put on the flexible panel, the locking member is held within the channel.
U.S. Pat. No. 3,273,497 shows another elongate strip type fastening device for a flexible panel. The patent shows the edge of a screen panel fastened to a frame by means of a two-piece fastening device including a flat bar member which sandwiches the screen into a receiving member, one end of which is concave for holding down one edge of the flat bar. The bar has a slot at one location on its edge opposite the concavity of the receiving member, and in a corresponding location on the receiving member is a protrusion over which the slot in the bar can pass. When the screen and locking bar have been inserted into the receiving member and are passed under the protrusion, the bar may be slid longitudinally to displace the slot from the protrusion, thereby locking the bar and the screen in position. The bar does not snap into the receiving member in an interference fit, nor is the bar tightly held within the receiving member.
Particularly in air inflatable structures consisting of panels of flexible plastic film, there is a need for an inexpensive, reliable and easily assembled fastener which will form an air-tight seal and also provide a means for holding the edge of the air inflatable structure to the ground or to another structure. See, for example, the co-pending allowed patent application of Frank E. Rom Ser. No. 450,424, filed Mar. 12, 1974, now U.S. Pat. No. 3,908,631, showing an air conduit including a plurality of layers which must be bound together in an elongate air-tight seam and also anchored to the ground for proper operation of the apparatus. The present invention described below is adaptable for use with such structures, as well as other air inflated structures requiring a reliable air-tight seam.
SUMMARY OF THE INVENTION
The present invention is a holding means, an edge connector and seam forming device for flexible films, relatively simple in structure and easily assembled to form an air-tight seam at the edges of plastic film layers. The fastening apparatus is advantageously used to hold in location and form the edge seals of air inflated structures. The invention eliminates the need for preformed perimeter seals on air structures, simplifying the overall manufacture and assembly operation and thus reducing construction and repair costs.
The apparatus consists of a pair of interfitting elongate extrusions, preferably of a relatively rigid plastic material but in any event of a slightly yieldable material. A locking extrusion is snapped into a base extrusion with the multiple film layers sandwiched therebetween. By the shape and relative sizing of the two extrusions, described in detail below, an air-tight film seal results. Attachment means are provided for fixing the apparatus and the seam formed thereby to the ground or other fixed structure.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing an air inflated structure employing the film connector of the invention;
FIG. 2 is an elevational sectional view taken along the line 2--2 of FIG. 1;
FIG. 3 is a perspective view showing the inner component of the film connector and the way in which it is connected to a tie-down line;
FIG. 4 is a perspective view showing the outer or base component of the film connector with the tie-down line passing therethrough;
FIG. 5 is an enlarged elevational sectional view showing the assembled film connector in engagement with multiple film layers; and
FIG. 6 shows the ends of two lengths of the connector which are joined by short sections to provide a continuous connector.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 of the drawings shows an inflated structure 10 employing a film connector 11 according to the invention to hold the structure 10 in position on the ground and to retain layers of plastic film 12 and 13 together in air-tight relationship. In the solar heat collector device which is used to illustrate the film connector of this invention, the film layer 12 is a transparent cover for the structure 10 while the layer 13 serves as a floor and is preferably of a dark, heat absorbent color. End panels 14 and 16, preferably folded from the bottom panel along a lower line 17 and sealed with the top transparent sheet along an upper arc 18, form air-tight ends on the structure 10.
The apparatus 10 further includes an inner conduit 21 of a dark, opaque film material, connected through an inner duct 22 with a blower (not shown). An outer duct 23, also connected to an air blower (not shown), communicates with the space defined interior of the film layers 12 and 13 and end panels 14 and 16, exterior of the inner conduit 21. Both the inner conduit 21 and the outer encasing conduit, which may be generally identified as 24, are thereby inflated while air travels through them toward the grain storage facility 19. At the downstream end of the structure 10, heated air from the inner conduit 21 and air from the outer encasing conduit 24, which is heated to a somewhat lesser extent, are emptied into a common effluent duct 26 which connects with the grain storage facility 19.
FIG. 2 shows the plastic film connectors 11 of the invention, indicating their manner of engagement with the plastic film layers 12 and 13 of the outer encasing conduit 24. The film connectors 11 comprise an inner locking component 27 and a base or outer component 28. As shown in FIG. 2, the connector is assembled by slipping a toe portion 29 of the locking component 27 into a rolled end 30 of the base component 28 with the film layers lying therebetween, and then snapping the inner component 27 down into the outer component 28. A hold-down line 31, which runs along the ground adjacent to the assembled film connector 11, is passed through the lower component 28 and connected with the upper component 27, as seen more clearly in reference to FIGS. 3, 4 and 5.
FIGS. 3, 4 and 5 show the individual locking and base components 27 and 28 of the plastic film connector 11 and their positions of engagement when assembled. Both components 27 and 28 preferably comprise elongate extrusions uniform in cross section throughout their length. The extrusions may be continuous throughout the length of the air heating apparatus 10, but since such structures may exceed 100 feet in length, it is preferred that the connector components be assembled from shorter lengths. The joints of the locking component may then be staggered from those of the base component, to aid in effective air sealing. Alternatively, as shown in FIG. 6, the components may be pre-assembled in nearly coextensive lengths with gaps 32 at predetermined locations to enable the structure 10 to be folded across its width. As FIG. 6 indicates, the base component 28 can extend farther into the gap 32 than the locking member 27, so that staggered joints result when closing sections 28a and 27a of the components are assembled on location.
As shown in FIG. 4, the lower or base component 28 is generally of a horizontal J shape, the rolled end 30 being positioned to receive the toe portion 29 of the locking component 27 (FIG. 3). The interior of the rolled end 30 is sized to accommodate the locking component 27 and the appropriate thickness of the film layers with narrow clearance so that the layers fit closely between the components, as shown in FIG. 5.
Extending from a flat portion 33 of the outer film connector component 28 is a latching strip 34 designed to engage and snap over a rear edge 36 of the locking component 27. Both components are formed from a material which is essentially rigid but possessing some degree of flexibility, such as rigid polyvinyl chloride, so that although the width of the inner locking component 27 is too large to permit the component to be freely inserted into the base component 28 with the film layers positioned between, both components are flexible enough to yield and allow the inner component 27 to snap into position in the base component 28 when assembled as shown at the left in FIG. 2.
As indicated in dashed lines in FIGS. 3, 4 and 5, the line 31 passes through a slotted hole 37 in the rearward end of the base film connector component 28 in looped fashion and is engaged in a pair of angled slots 38 in a vertically extending portion 39 of the locking member 27. The term "line" as used herein and in the appended claims may be considered to include any relatively flexible securing means such as hemp or plastic rope, wire, cable or chain. The line 31 is preferably continuous throughout the length of one side of the inflatable apparatus 10, and after it has been assembled to the connector 11 as shown in the figures, it is drawn taut throughout its length and staked to the ground at several locations alongside the film connector. In this way, the entire inflatable apparatus 10 is securely fastened to the ground to prevent movement and damage by wind. The manner in which the line connects to the locking member 27, via the vertically extending portion 39, helps retain the film connector 11 tightly assembled. By pulling the locking member 27 at a downwardly and rearwardly inclined angle, the line 31 helps prevent inadvertent releasing and removal of the locking member from the base member 28.
The plastic film connector 11 keeps the edges of the film layers 12 and 13 tightly retained together throughout their length so that substantially all leakage of air between the layers is prevented. This is accomplished through several design features of the film connector. The rolled end 30 of the base component 28, which is rolled through more than 180° and preferably through about 270° as seen in FIG. 5, contributes in several ways to making the film layers air tight. The fact that the layers of film must together curl around the rolled end 30 and under its tip causes the layers to be put in intimate contact in the area of the tip. The inflation of the outer encasing conduit 24 adds to this effect by putting the layers 12 and 13 into tension, forcing them more tightly together at the tip of the rolled end 30. Intimate contact between the layers is also effected at the tip of the toe portion 29 of the locking member when the layers are in tension. Another effect of the rolled end 30 is the result of the deep interior cavity 41 which is formed thereby. Besides forming a socket for engagement with the toe 29 of the locking member 27 to initiate the assembly of the two components, the deep cavity assures greater contact between the film layers when the locking member 27 is engaged in the cavity. By providing more surface area for sandwiching of the film layers between the components, greater contact and a better air-tight relationship between the layers is established.
If in the assembled apparatus 10, joints between sections of the components 27 and 28 are staggered as discussed above (e.g., as shown in FIG. 6), then air-tight contact between the layers is maintained. Since the layers tightly contact one another at both the tip of the rolled end 30 and the tip of the toe portion 29, and since one of the components is continuous where the other is interrupted, the air-tight relationship is maintained.
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A device for releasably retaining together in air-tight relationship the edges of a plurality of film layers which may be used, for example, in an inflatable structure. The device includes a pair of elongate strips, one of which is snapped into the other with the edges of the film layers positioned therebetween, thereby forming a seam at the film edges. The strips are preferably extruded shapes which are coextensive in length with the edges of the film to be sealed together. Means are provided for anchoring the strips to the ground after they have been engaged with the film layer edges, with the anchor means designed to enhance the locking force placed on the device.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
One aspect of the present invention relates to a telephoto zoom lens suited for a single-lens reflex camera and, more particularly, to a compact telephoto zoom lens which has a focal length at the wide-angle end, which is about 1.4 to 2 times of the diagonal length of an effective frame, and has a zoom ratio exceeding ×2.5. Another aspect of the present invention relates to a compact inner-focus type zoom lens which is suited for an auto-focus type single-lens reflex camera and has a zoom ratio exceeding ×2.5.
2. Related Background Art
As conventional telephoto zoom lenses having a zoom ratio exceeding ×2.5, (1) a four-group afocal zoom lens comprising positive, negative, positive, and positive lens groups, (2) a double telephoto type four-group zoom lens comprising positive, negative, positive, and negative lens groups, (3) a three-group zoom lens comprising positive, negative, and positive lens groups, and the like have been proposed. The four-group afocal zoom lens is suitable for a high-performance lens since the functions of the four lens groups are clearly distinguished from each other. The double telephoto type zoom lens is suitable for achieving a short total length since an enlargement magnification is provided by adopting a negative lens group as the fourth lens group. The three-group zoom lens is suitable for achieving a compact and low-cost structure since the number of lens groups is small.
However, the four-group afocal zoom lens has a fixed total length from the wide-angle end to the telephoto end, and it is difficult to shorten the total length. For this reason, the four-group afocal zoom lens tends to be large in size and heavy, and is not advantageous in portability. On the other hand, in the double telephoto type zoom lens, the total length at the wide-angle end can be smaller than that at the telephoto end, and portability can be improved. However, since the double telephoto type zoom lens requires four lens groups, the lens barrel structure is complicated, and cost cannot be sufficiently reduced. The three-group zoom lens (3) comprising positive, negative, and positive lens groups is suitable for achieving a low-cost structure, and can shorten the total length at the wide-angle end since the number of lens groups is as small as three. Also, this zoom lens is advantageous in portability. Such a zoom lens is proposed by, e.g., Japanese Patent Application Laid-Open No. 63-118116.
As a conventional focusing method of a zoom lens, a one-group extension method for moving the first lens group is known. This one-group extension method has a merit that moving amounts upon focusing to a given distance are equal to each other at the wide-angle end and the telephoto end, and is conventionally widely used as a focusing method of a zoom lens.
However, with the one-group extension focusing method, when an object at a near distance is to be focused, since the first lens group largely moves in the object direction, the vignetting in such a near distance phototaking state tends to be large, and in order to obtain a small vignetting even in the near distance phototaking state, the size of the first lens group must be increased. For this reason, this results in an increase in lens diameter and an increase in size of the entire zoom lens. Furthermore, when a zoom lens adopting this focusing method is attached to an auto-focus type camera and an auto-focus operation is to be performed, the first lens group as a large, heavy lens group must be moved, and it is difficult to achieve high-speed focusing.
SUMMARY OF THE INVENTION
It is an object of the present invention to achieve, in its first aspect, a more compact three-group zoom type telephoto zoom lens comprising positive, negative, and positive lens groups, which lens is advantageous in term of achieving a compact structure and low cost, than the prior art.
A telephoto zoom lens according to the first aspect of the present invention comprises, in the following order from the object side, a first lens group having a positive refracting power, a second lens group having a negative refracting power, and a third lens group having a positive refracting power, wherein upon zooming from the wide-angle end to the telephoto end, at least the first and third lens groups move in the object direction, an air distance between the first and second lens groups increases, and an air distance between the second and third lens groups decreases. The telephoto zoom lens satisfies the following conditions:
1.25≦f1/fW≦1.50 (1)
-0.37≦f2/fW≦-0.30 (2)
0.37≦f3/fW≦0.46 (3)
where f1 is the focal length of the first lens group, f2 is the focal length of the second lens group, f3 is the focal length of the third lens group, and fW is the focal length of the entire system at the wide-angle end.
The third lens group comprises, in the following order from the object side, a first lens subgroup having a positive refracting power and a second lens subgroup having a negative refracting power, and preferably satisfies the following conditions:
-5≦f3b/f3≦-3 (4)
0.3≦D/fW≦0.6 (5)
where f3b is the focal length of the second lens subgroup, and D is the air distance between the first and second lens subgroups.
Furthermore, the first lens subgroup comprises, in the following order from the object side, two double-convex positive lens components, and a meniscus-shaped lens component having a concave surface facing the image side, and the second lens subgroup comprises, in the following order from the object side, a negative meniscus lens having a concave surface facing the object side, and a positive lens having a convex surface facing the image side. If the imaging magnification of the second lens subgroup at the wide-angle end is represented by β3b, it preferably satisfies:
1.2=β3b≦1.7 (6)
The present invention adopts a simple structure comprising positive, negative, and positive lens groups, and the total length at the wide-angle end is decreased by moving the first lens group to the object side upon zooming from the wide-angle end to the telephoto end. Since the third lens group is moved upon zooming from the wide-angle end to the telephoto end, the third lens group also shares a zoom function, and hence, a change in imaging magnification of the second lens group can be small as compared to the zoom ratio, thus reducing variations of various aberrations upon zooming.
The respective condition formulas of the present invention will be explained below.
Condition formula (1) is associated with achieving a decrease in total length of the zoom lens, and defines a proper range of the focal length f1 of the first lens group. When the focal length f1 exceeds the upper limit of condition formula (1), the focal length of the first lens group is-prolonged, and hence, the total length of the zoom lens undesirably increases contrary to the object of the present invention. 0n the contrary, when the focal length f1 becomes smaller than the lower limit of condition formula (1), the focal length of the first lens group is shortened, and the back focus of the first lens group alone decreases accordingly. As a result, a possible maximum distance range between the first and second lens groups is narrowed, and it becomes difficult to obtain a high zoom ratio. Furthermore, it becomes difficult to correct various aberrations such as a spherical aberration, an astigmatism, and the like with good balance.
Condition formula (2) is associated with attaining a high zoom ratio of the zoom lens, and defines a proper range of the focal length f2 of the second lens group. When the focal length f2 becomes smaller than the lower limit of condition formula (2), the focal length of the second lens group increases in the negative direction, and it becomes difficult to obtain a high zoom ratio under condition formula (1). On the contrary, when the focal length exceeds the upper limit of condition formula (2), the focal length of the second lens group decreases in the negative direction, and it becomes difficult to suppress variations of various aberrations such as a spherical aberration, an astigmatism, a distortion, and the like upon zooming.
Condition formula (3) is associated with obtaining a decrease in total length of the zoom lens, and defines a proper range of the focal length f3 of the third lens group. When the focal length f3 exceeds the upper limit of condition formula (3), the focal length of the third lens group is prolonged, and the distance between two conjugate points associated with the third lens group (an object point for the third lens group, i.e., an image point defined by the first and second lens groups, and an image point for the third lens group, i.e., an image point of the entire zoom lens system) increases, resulting an increase in total length of the zoom lens. Contrary to this, when the focal length f3 becomes smaller than the lower limit of condition formula (3), the focal length of the third lens group is shortened, and it becomes difficult to correct various aberrations such as a spherical aberration, and the like with good balance. Also, the back focus at the wide-angle end is shortened, and the zoom lens is not suitable for a single-lens reflex camera.
In the present invention, as described above, in order to further decrease the total length, it is desirable that the third lens group G3 comprise, in the following order from the object side, a first lens subgroup G3a having a positive refracting power and a second lens subgroup G3b having a negative refracting power. With this arrangement, the third lens group can have a telephoto type structure, and the total length of the zoom lens can be shortened. In addition, since the negative second lens subgroup generates a positive distortion, a negative distortion which is likely to be generated by the negative second lens group can be canceled. At this time, it is desirable to satisfy condition formulas (4) and (5).
When the focal length of the second lens subgroup becomes smaller than the lower limit of condition formula (4), the focal length of the second lens subgroup increases in the negative direction, and the effect obtained upon employment of a telephoto type third lens group becomes weak, resulting in an increase in total length. Contrary to this, when the focal length of the second lens subgroup exceeds the upper limit of condition formula (4), the focal length of the second lens subgroup decreases in the negative direction, and it becomes difficult to satisfactorily correct various aberrations such as a spherical aberration, and the like. Furthermore, the back focus at the wide-angle end is shortened, and the zoom lens is not suitable for a single-lens reflex camera.
Condition formula (5) defines an optimal range of the air distance between the first and second lens subgroups under condition formula (4). When the air distance exceeds the upper limit of condition formula (5), the total length of the third lens group increases, and it becomes difficult to decrease the total length of the zoom lens. Contrary to this, when the air distance becomes smaller than the lower limit of condition formula (5), it becomes difficult to correct a negative distortion which tends to be generated by the second lens group.
Furthermore, in order to satisfactorily correct various aberrations, it is desirable that the first lens subgroup G3a comprise, in the following order from the object side, two double-convex positive lens components, and a meniscus-shaped lens component having a concave surface facing the image side, and the second lens subgroup G3b comprise, in the following order from the object side, a negative meniscus lens having a concave surface facing the object side, and a positive lens having a convex surface facing the image side.
In order to reliably decrease the total length under condition formulas (4) and (5), it is desirable to satisfy condition formula (6).
When the imaging magnification of the second lens subgroup becomes smaller than the lower limit of condition formula (6), the effect obtained upon employment of a telephoto type third lens group becomes weak, resulting in an increase in total length. On the contrary, when the imaging magnification exceeds the upper limit of condition formula (6), the effect obtained upon employment of a telephoto type third lens group becomes excessive, and it becomes difficult to correct various aberrations such as a spherical aberration, and the like.
In the first lens subgroup, in order to correct various aberrations such as a spherical aberration, an on-axis chromatic aberration, and the like with good balance, it is desirable that the first lens subgroup comprise, in the following order from the object side, a double-convex positive lens, a cemented positive lens constituted by a double-convex positive lens L32 and a negative meniscus lens L33, and a cemented positive lens constituted by a double-convex positive lens L34 and a double-concave negative lens L35, and it is also desirable that a stop be arranged immediately after the first lens subgroup.
At this time, in order to satisfactorily correct a spherical aberration and to obtain a proper Petzval's sum, it is desirable to satisfy the following condition formulas:
n33-n32≧0.2 (7)
n35-n34≧0.2 (8)
where n32 is the refractive index of the double-convex positive lens, n33 is the refractive index of the negative meniscus lens L33, n34 is the refractive index of the double-convex positive lens L34, and n35 is the refractive index of the double-concave negative lens L35.
In order to achieve both the compact zoom lens and correction of various aberrations, it is desirable that a stop be arranged to be movable together with the third lens group.
In order to satisfactorily correct an on-axis chromatic aberration, it is desirable to satisfy the following condition formulas:
ν32-ν33≧10 (9)
ν34-ν35≧25 (10)
where ν32 is the Abbe's number of the double-convex positive lens L32, ν33 is the Abbe's number of the negative meniscus lens L33, ν34 is the Abbe's number of the double-convex positive lens L34, and ν35 is the Abbe's number of the double-concave negative lens L35.
It is an object of the present invention to achieve, in its second aspect, a compact lens system, and satisfactory correction of various aberrations upon zooming and focusing when a three-group zoom lens comprising positive, negative, and positive lens groups adopts an inner-focus type for moving the second lens group, which is advantageous in auto-focus and a compact structure.
In the case of the three-group zoom lens comprising positive, negative, and positive lens groups like in the present invention, since a light beam is most converged in the second lens group, the second lens group has the smallest diameter and is lightweight. For this reason, focusing is performed using the second lens group. Such a focusing method is advantageous in high-speed focusing in an auto-focus operation as compared to focusing using the first lens group or the third lens group.
An inner-focus type zoom lens according to the second aspect of the present invention comprises, in the following order from the object side, a first lens group having a positive refracting power, a second lens group having a negative refracting power, and a third lens group having a positive refracting power, wherein, upon zooming from the wide-angle end to the telephoto end, at least the first and third lens groups move in the object direction, the air distance between the first and second lens groups increases, and the air distance between the second and third lens groups decreases, and, upon focusing from a far-distance object to a near-distance object, the second lens group moves in the object direction. The zoom lens satisfies the following conditions:
0.5≦|β2T|0.8, for β2T<0 (11)
1.2≦β3T/β3W≦2.0 (12)
where β2T is the imaging magnification of the second lens group at the telephoto end, β3W is the imaging magnification of the third lens group at the wide-angle end, and β3T is the imaging magnification of the third lens group at the telephoto end.
When the focal length of the first lens group is represented by f1, the focal length of the second lens group is represented by f2, and the focal length of the entire system when the zoom lens is at the wide-angle end is represented by fW, it is preferable to satisfy the following conditions:
1.1≦f1/fW≦1.7 (13)
0.30≦|f2|/fW≦0.43; for f2<0(14)
Also, the following condition is preferably satisfied:
2.0 ≦|β3T|≦3.2; for β3T<0(15)
Furthermore, a stop according to the present invention is arranged to be movable together with the third lens group.
The present invention adopts a simple structure comprising positive, negative, and positive lens groups, and the total length at the wide-angle end is decreased by moving the first lens group to the object side upon zooming from the wide-angle end to the telephoto end. Since focusing is performed by moving the compact, lightweight second lens group, a compact lens system and a high focusing speed in an auto-focus operation can be realized.
Since the third lens group is moved upon zooming from the wide-angle end to the telephoto end, the third lens group also shares a zoom function, and hence, a change in imaging magnification of the second lens group can be small as compared to the zoom ratio, thus eliminating variations of various aberrations upon zooming and focusing. The respective condition formulas will be explained below.
Condition formula (11) defines a proper range of the imaging magnification β2T of the second lens group at the telephoto end when focusing is performed using the second lens group. When the imaging magnification exceeds the upper limit of condition formula (11), the moving amount upon focusing of the second lens group at the telephoto end increases, and it becomes difficult to sufficiently decrease the shortest phototaking distance. When the imaging magnification β2 of the second lens group is an equal magnification (β2 =-1), focusing is disabled. On the contrary, when the imaging magnification becomes smaller than the lower limit of condition formula (11), the divergent function of the second lens group at the telephoto end becomes excessive, and the total length of the zoom lens undesirably increases.
In the zoom lens according to the second aspect of the present invention, the zooming function is shared not only by the second lens group but also by the third lens group. For this reason, a change in imaging magnification of the second lens group can become small as compared to the zoom ratio, and variations of various aberrations generated in the second lens group upon zooming and focusing can be suppressed. Condition formula (12) defines a proper range for the change ratio in imaging magnification of the third lens group at that time.
When the change ratio becomes smaller than the lower limit of condition formula (12), the zooming function shared by the third lens group becomes small, and a change in imaging magnification of the second lens group increases. For this reason, variations of various aberrations upon zooming and focusing, in particular, variations of a curvature of field and an astigmatism become undesirably large. On the contrary, when the change ratio exceeds the upper limit of condition formula (12), a change in imaging magnification of the third lens group becomes excessive, and variations of various aberrations in the third lens group occur. As a result, it becomes difficult to correct aberrations. Furthermore, when the stop is arranged together with the third lens group, full-open f-numbers at the wide-angle end and the telephoto end become largely different from each other, and the full-open f-number at the telephoto end tends to be large.
Furthermore, in a three-group inner-focus type zoom lens comprising positive, negative, and positive lens groups, when the focal length at the wide-angle end is set to be about 1.3 to 3 times of the diagonal length of an effective frame, and a zoom ratio exceeding ×2.5 is to be obtained, it is desirable to satisfy conditions given by condition formulas (13) and (14).
Condition formula (13) is associated with a decrease in total length of the zoom lens, and defines a proper range of the focal length f1 of the first lens group. When the focal length f1 exceeds the upper limit of condition formula (13), the focal length of the first lens group is prolonged, and hence, the total length of the zoom lens undesirably increases. On the contrary, when the focal length f1 becomes smaller than the lower limit of condition formula (13), the focal length of the first lens group is shortened, and the back focus of the first lens group alone decreases accordingly. As a result, a possible maximum distance range between the first and second lens groups is narrowed, and it becomes difficult to obtain a high zoom ratio. Furthermore, it becomes difficult to correct various aberrations such as a spherical aberration, an astigmatism, and the like with good balance.
Condition formula (14) is associated with a high zoom ratio of the zoom lens, and defines a proper range of the focal length f2 of the second lens group. When the focal length f2 exceeds the upper limit of condition formula (14), the focal length of the second lens group increases in the negative direction, and it becomes difficult to obtain a high zoom ratio under condition formula (13). On the contrary, when the focal length f2 becomes smaller than the lower limit of condition formula (14), the focal length of the second lens group decreases in the negative direction, and it becomes difficult to suppress variations of various aberrations such as a spherical aberration, an astigmatism, a distortion, and the like upon zooming and focusing.
Furthermore, in order to achieve a compact zoom lens, it is desirable to satisfy condition formula (15).
Condition formula (15) is associated with a decrease in total length of the zoom lens, and defines a proper range of the imaging magnification β3T of the third lens group at the telephoto end. When the imaging magnification becomes smaller than the lower limit of condition formula (15), the imaging magnification of the third lens group at the telephoto end decreases in the negative direction, and the telephoto function of the zoom lens as a whole becomes small, resulting in an increase in total length of the zoom lens. On the contrary, when the imaging magnification exceeds the upper limit of condition formula (15), the imaging magnification of the third lens group at the telephoto end increases in the negative direction, and various aberrations generated in the first and second lens groups are enlarged by the third lens group. As a result, it becomes difficult to correct various aberrations such as a spherical aberration and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a lens diagram showing the first embodiment of a zoom lens according to the present invention;
FIG. 2 is a lens diagram showing the second embodiment of a zoom lens according to the present invention;
FIG. 3 is a lens diagram showing the third embodiment of a zoom lens according to the present invention; and
FIG. 4 is a lens diagram showing the fourth embodiment of a zoom lens according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first and second embodiments according to the first aspect of the present invention will be described below.
[First Embodiment]
FIG. 1 is a lens diagram showing the first embodiment. The zoom lens of the first embodiment comprises, in the following order from the object side: a first lens group G1 which has a positive refracting power and is constituted by a cemented positive lens consisting of a negative meniscus lens L11 and a double-convex lens L12, and a double-convex positive lens L13; a second lens group G2 which has a negative refracting power and is constituted by a cemented negative lens consisting of a double-concave negative lens L21 and a positive meniscus lens L22, and a double-concave negative lens L23 having a concave surface with a smaller radius of curvature facing the object side; and a third lens group G3 which has a positive refracting power and is constituted by a first lens subgroup G3a having a positive refracting power and constituted by a double-convex positive lens L31, a cemented positive lens which is a double-convex positive lens as a cemented lens unit and consists of a double-convex positive lens L32 and a negative meniscus lens L33, and a cemented positive lens which is a meniscus lens as a cemented lens unit and consists of a double-convex positive lens L34 and a double-concave negative lens L35, a stop S, and a second lens subgroup G3b having a negative refracting power and constituted by a negative meniscus lens L36 having a concave surface facing the object side and a positive meniscus lens L37 having a convex surface facing the image plane side.
Upon zooming from the wide-angle end to the telephoto end, the first and third lens groups G1 and G3 move together in the object direction, the second lens group G2 moves closer to the object at least at the telephoto end than at the wide angle end, the air distance between the first and second lens groups G1 and G2 increases, and the air distance between the second and third lens groups G2 and G3 decreases. FIG. 1 shows the lens positions at the wide-angle end, and arrows indicate the moving loci of the lens groups upon zooming from the wide-angle end to the telephoto end.
In the first embodiment, focusing from a far distance to a near distance is performed by moving the second lens group G2 in the object direction. Since the second lens group G2 is used for focusing, the lens diameter of the first lens group can be decreased, and the closest phototaking distance can be shortened.
Table 1 below summarizes data values according to the first embodiment of the present invention. In the data table of this embodiment, f is the focal length, F is the f-number, and 2ωis the field angle. In addition, numeral i in the leftmost column is the order of the lens surface from the object side, r is the radius of curvature of the lens surface, d is the lens surface interval, and n and v are the values of the refractive index and the Abbe's number in correspondence with the d-line (λ=587.6 nm).
TABLE 1______________________________________f = 70.60 to 202.44F = 4.09 to 5.682ω = 35.2 to 11.9°i r d ν n______________________________________ 1 90.2192 1.875 23.0 1.86074 2 56.4067 5.625 64.1 1.51680 3 -3207.9350 .125 4 108.5369 4.000 56.4 1.50137 5 -302.2972 (d5) 6 -82.6007 1.375 58.5 1.65160 7 19.9831 3.750 23.0 1.86074 8 37.1254 3.625 9 -42.4576 1.375 49.4 1.7727910 3344.2110 (d10)11 379.7595 4.000 59.0 1.5182312 -37.9647 .12513 153.5445 4.625 59.0 1.5182314 -36.1209 1.375 40.9 1.7963115 -105.0394 .37516 23.1575 7.250 64.1 1.5168017 -65.7760 1.375 25.5 1.8045818 168.9502 2.75019 ∞ 28.918 (stop)20 -15.1836 1.500 46.5 1.8041121 -28.2829 .12522 -278.6342 3.375 25.8 1.7847223 -47.8903 (B.f)(Variable Interval Upon Zooming)f 70.5987 133.3121 202.4442d5 4.5707 28.4524 35.0774d10 16.1257 7.7669 1.6901B.f 41.7660 51.9255 69.3959(Condition Corresponding Value) (1) f1/fW = 1.452 (2) f2/fW = -0.351 (3) f3/fW = 0.436 (4) f3b/f3 = -3.89 (5) D/fW = 0.449 (6) β3b = 1.441 (7) n33 - n32 = 0.27808 (8) n35 - n34 = 0.28778 (9) ν32 - ν33 = 18.1 (10) ν34 - ν35 = 38.6______________________________________
[Second Embodiment]
FIG. 2 is a lens diagram showing the second embodiment. The zoom lens of this embodiment comprises, in the following order from the object side: a first lens group G1 which has a positive refracting power and is constituted by a cemented positive lens consisting of a negative meniscus lens L111 and a double-convex lens L112, and a double-convex positive lens L113; a second lens group G2 which has a negative refracting power and is constituted by a cemented negative lens consisting of a double-concave negative lens L121 and a positive meniscus lens L122, and a double-concave negative lens L123 having a concave surface with a smaller radius of curvature facing the object side; and a third lens group G3 which has a positive refracting power and is constituted by a first lens subgroup G3a having a positive refracting power and constituted by a double-convex positive lens L131, a cemented positive lens which consists of a double-convex positive lens L132 and a negative meniscus lens L133, and a cemented positive lens which consists of a double-convex positive lens L134 and a double-concave negative lens L135, a stop S, and a second lens subgroup G3b having a negative refracting power and constituted by a negative meniscus lens L136 having a concave surface facing the object side and a positive meniscus lens L137 having a convex surface facing the image plane side.
Upon zooming from the wide-angle end to the telephoto end, the first and third lens groups G1 and G3 move together in the object direction, the second lens group G2 moves closer to the object at least at the telephoto end than at the wide angle end, the air distance between the first and second lens groups G1 and G2 increases, and the air distance between the second and third lens groups G2 and G3 decreases. FIG. 2 shows the lens positions at the wide-angle end, and arrows indicate the moving loci of the lens groups upon zooming from the wide-angle end to the telephoto end.
In the second embodiment, focusing from a far distance to a near distance is performed by moving the first lens group G1 in the object direction.
Table 2 below summarizes data values according to the second embodiment of the present invention. In the data table of this embodiment, f is the focal length, F is the f-number, and 2ω is the field angle. In addition, numeral i in the leftmost column is the order of the lens surface from the object side, r is the radius of curvature of the lens surface, d is the lens surface interval, and n and νare the values of the refractive index and the Abbe's number in correspondence with the d-line (λ=587.6 nm).
TABLE 2______________________________________f = 70.60 to 202.44F = 4.10 to 5.742ω = 35.1 to 11.9°i r d ν n______________________________________ 1 83.7390 1.875 23.0 1.86074 2 53.8424 7.000 64.1 1.51680 3 -3445.3237 .125 4 120.0309 4.875 56.4 1.50137 5 -296.2943 (d5) 6 -82.9140 1.375 58.5 1.65160 7 20.0337 3.750 23.0 1.86074 8 37.4080 3.625 9 -43.0096 1.375 49.4 1.7727910 1223.8375 (d10)11 503.8516 4.000 59.0 1.5182312 -36.7397 0.12513 106.4352 4.625 59.0 1.5182314 -38.0556 1.375 40.9 1.7963115 -137.0427 .37516 23.1807 7.250 64.1 1.5168017 -69.6115 1.375 25.5 1.8045818 149.8504 2.75019 ∞ 28.921 (stop)20 -15.1875 1.500 46.5 1.8041121 -28.1687 .12522 -194.2505 3.375 25.8 1.7847223 -45.1040 (B.f)(Variable Interval Upon Zooming)f 70.5993 133.3080 202.4385d5 3.4404 26.9470 33.5720d10 16.4234 8.0716 2.0628B.f 41.5074 52.2703 70.0546(Condition Corresponding Value) (1) f1/fW = 1.452 (2) f2/fW = -0.351 (3) f3/fW = 0.436 (4) f3b/f3 -3.89 (5) D/fW = 0.449 (6) β3b = 1.441 (7) n33 - n32 = 0.27808 (8) n35 - n34 = 0.28778 (9) ν32 - ν33 = 18.1 (10) ν34 - ν35 = 38.6______________________________________
As described above, according to the first aspect of the present invention, a high-performance telephoto zoom lens, which has a compact structure and a high zoom ratio, and is suitable for a single-lens reflex camera, can be achieved.
Note that by decentering one of the first, second, and third lens groups of the telephoto zoom lens according to the first aspect of the present invention in a direction perpendicular to the optical axis, the vibration of the zoom lens as a whole can be canceled, and the image can be stabilized.
The third and fourth embodiments according to the second aspect of the present invention will be described below.
[Third Embodiment]
FIG. 3 is a lens diagram showing the third embodiment. The zoom lens of this embodiment comprises, in the following order from the object side: a first lens group G1 which has a positive refracting power and is constituted by a cemented positive lens consisting of a negative meniscus lens L211 and a double-convex positive lens L212, and a double-convex positive lens L213; a second lens group G2 which has a negative refracting power and is constituted by a cemented negative lens consisting of a double-concave negative lens L221 and a positive meniscus lens L222, and a double-concave negative lens L223 having a concave surface with a smaller radius of curvature facing the object side; and a third lens group G3 which has a positive refracting power and is constituted by a double-convex positive lens L231, a cemented positive lens which consists of a double-convex positive lens L232 and a negative meniscus lens L233, a cemented positive lens which consists of a double-convex positive lens L234 and a double-concave negative lens L235, a stop S, a negative meniscus lens L236 having a concave surface facing the object side, and a positive meniscus lens L237 having a convex surface facing the image plane side. Upon zooming from the wide-angle end to the telephoto end, the first and third lens groups G1 and G3 move together in the object direction, the second lens group G2 moves closer to the object at least at the telephoto end than at the wide angle end, the air distance between the first and second lens groups G1 and G2 increases, and the air distance between the second and third lens groups G2 and G3 decreases. FIG. 3 shows the lens positions at the wide-angle end, and arrows indicate the moving loci of the lens groups upon zooming from the wide-angle end to the telephoto end. Focusing from a far distance to a near distance is performed by moving the second lens group G2 in the object direction.
Table 3 below summarizes data values according to the third embodiment of the present invention. In the data table of this embodiment, f is the focal length, F is the f-number, and 2ω is the field angle. In addition, numeral i in the leftmost column is the order of the lens surface from the object side, r is the radius of curvature of the lens surface, d is the lens surface interval, and n and νare the values of the refractive index and the Abbe's number in correspondence with the d-line (λ=587.6 nm).
TABLE 3______________________________________f = 70.60 to 202.44F = 4.09 to 5.682ω = 35.2 to 11.9°i r d ν n______________________________________ 1 90.2192 1.875 23.0 1.86074 2 56.4067 5.625 64.1 1.51680 3 -3207.9350 .125 4 108.5369 4.000 56.4 1.50137 5 -302.2972 (d5) 6 -82.6007 1.375 58.5 1.65160 7 19.9831 3.750 23.0 1.86074 8 37.1254 3.625 9 -42.4576 1.375 49.4 1.7727910 3344.2110 (d10)11 379.7595 4.000 59.0 1.5182312 -37.9647 .12513 153.5445 4.625 59.0 1.5182314 -36.1209 1.375 40.9 1.7963115 -105.0394 .37516 23.1575 7.250 64.1 1.5168017 -65.7760 1.375 25.5 1.8045818 168.9502 2.75019 ∞ 28.918 (stop)20 -15.1836 1.500 46.5 1.8041121 -28.2829 .12522 -278.6342 3.375 25.8 1.7847223 -47.8903 (B.f)(Variable Interval Upon Zooming)f 70.5987 133.3121 202.4442d5 4.5707 28.4524 35.0774d10 16.1257 7.7669 1.6901B.f 41.7660 51.9255 69.3959(Variable Interval When Imaging Magnification β = -0.025)f 70.5987 133.3121 202.4442β -.0250 -.0250 -.0250R 2873.1962 5195.7597 7756.1834d5 3.9272 27.3067 33.6715d10 16.7692 8.9126 3.0960B.f 41.7660 51.9255 69.3958(Condition Corresponding Value) (11) β2T = -0.736 (12) β3T/β3W = 1.503 (13) f1/fW = 1.452 (14) f2/fW = -0.351 (15) β3T = -2.683______________________________________
[Fourth Embodiment]
FIG. 4 is a lens diagram of the fourth embodiment. The zoom lens of this embodiment comprises, in the following order from the object side: a first lens group G1 which has a positive refracting power and is constituted by a cemented positive lens consisting of a negative meniscus lens L311 and a double-convex positive lens L312, and a positive meniscus lens L313 having a convex surface facing the object side; a second lens group G2 which has a negative refracting power and is constituted by a cemented negative lens consisting of a double-concave negative lens L321 and a positive meniscus lens L322, and a double-concave negative lens having a concave surface with a smaller radius of curvature facing the object side; and a third lens group G3 which has a positive refracting power and is constituted by a double-convex positive lens L331, a cemented positive lens consisting of a double-convex positive lens L332 and a double-concave negative lens L333, a positive meniscus lens L334 having a convex surface facing the object side, a stop S, a negative meniscus lens L335 having a concave surface facing the object side, and a double-convex positive lens L336 having a convex surface with a higher radius of curvature facing the image plane side.
Upon zooming from the wide-angle end to the telephoto end, the first and third lens groups G1 and G3 move together in the object direction, the second lens group G2 moves closer to the object at least at the telephoto end than at the wide angle end, the air distance between the first and second lens groups G1 and G2 increases, and the air distance between the second and third lens groups G2 and G3 decreases. FIG. 4 shows the lens positions at the wide-angle end, and arrows indicate the moving loci of the lens groups upon zooming from the wide-angle end to the telephoto end. Focusing from a far distance to a near distance is performed by moving the second lens group G2 in the object direction.
Table 4 below summarizes data values according to the fourth embodiment of the present invention. In the data table of this embodiment, f is the focal length, F is the f-number, and 2ω is the field angle. In addition, numeral i in the leftmost column is the order of the lens surface from the object side, r is the radius of curvature of the lens surface, d is the lens surface interval, and n and νare the values of the refractive index and the Abbe's number in correspondence with the d-line (λ=587.6 nm).
TABLE 4______________________________________f = 70.60 to 202.43F = 4.00 to 5.682ω = 35.1 to 11.9°i r d ν n______________________________________ 1 88.1409 1.875 23.0 1.86074 2 57.3386 6.500 64.1 1.51680 3 -240.0927 .125 4 133.2533 3.125 54.6 1.51454 5 762.7255 (d5) 6 -129.5266 1.375 58.5 1.65160 7 20.7128 3.500 23.0 1.86074 8 41.5763 3.875 9 -44.7701 1.375 46.5 1.8041110 247.9675 (d10)11 109.4866 5.000 49.0 1.5317212 -36.4263 .12513 49.5668 6.375 64.1 1.5168014 -28.3293 1.375 27.6 1.7552015 1240.2446 .37516 20.5191 3.500 64.1 1.5168017 35.9424 2.75018 ∞ 29.000 (stop)19 -14.3107 1.500 46.8 1.7668420 -26.2535 .12521 1451.1245 3.375 25.5 1.8045822 -61.7409 (B.f)(Variable Interval Upon Zooming)f 70.6039 133.2734 202.4283d5 3.2658 29.7002 36.9403d10 16.1032 7.4697 1.1666B.f 40.2607 49.8480 66.6864(Variable Interval When Imaging Magnification β = -0.025)f 70.6039 133.2734 202.4283β -.0250 -.0250 -.0250R 2868.5019 5190.2746 7764.9349d5 2.5739 28.4908 35.5026d10 16.7952 8.6791 2.6043B.f 40.2607 49.8480 66.6864(Condition Corresponding Value) (11) β2T = -0.711 (12) β3T/β3W = 1.503 (13) f1/fW = 1.567 (14) f2/fW = -0.374 (15) β3T = -2.571______________________________________
As described above, according to the second aspect of the present invention, a high-performance inner-focus type zoom lens, which has a compact structure and a high zoom ratio, and is suitable for a single-lens reflex camera, can be achieved.
Note that by decentering one of the first, second, and third lens groups of the inner-focus type zoom lens according to the second aspect of the present invention in a direction perpendicular to the optical axis, the vibration of the zoom lens as a whole can be canceled, and the image can be stabilized.
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A telephoto zoom lens includes, in the following order from the object side, a first lens group having a positive refracting power, a second lens group having a negative refracting power, and a third lens group having a positive refracting power. Upon zooming from the wide-angle end to the telephoto end, at least the first and third lens groups move in the object direction, the air distance between the first and second groups increases, and the air distance between the second and third lens groups decreases. The telephoto zoom lens satisfies the following conditions:
1.25≦f1/fW≦1.50
-0.37≦f2/fW≦-0.30
0.37≦f3/fW≦0.46
where f1 is the focal length of the first lens group, f2 is the focal length of the second lens group, f3 is the focal length of the third lens group, and fW is the focal length of the entire system at the wide-angle end.
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CROSS REFERENCE
The present patent application is a continuation-in-part to our prior U.S. patent application Ser. No. 12/928,231 filed Dec. 7, 2010 now U.S. Pat. No. 8,584,566.
TECHNICAL FIELD
The present invention relates generally to an apparatus for cleaning the cores of rolls of sheet form material. After the sheet form material is unwound from the core, remaining scrap sheet form material is removed and the used core is inspected. Good cores are returned to be re-used and rejected cores are disposed of.
BACKGROUND OF THE INVENTION
Many products are manufactured from elongated sheet or stock material that is shipped and stored in the form of a roll or coil. Continuous strips or webs of thin, flexible material are commonly provided wound on cores to provide rolls of sheet material. The rolls of sheet material are subsequently unwound for production of items made from the materials. Examples of these materials are plastic film, metal foil, tissue and paper.
During the manufacture of products using the sheet material, the sheet or stock material is unwound from the core. If the outer surface of the roll of sheet material is damaged or unusable, the outer surface of material must be removed to expose fresh new material. Also, after the sheet material is unwound, remnants of material remain on the cores of the rolls. In order to properly recycle and use the cores, the remnants of material must be cleaned off the core and the core must be inspected for any damage which would make the core unusable.
Such cores are valuable, particularly, if they can be recycled or reused. It is commonplace for there to be a large number and variety of cores containing various types of sheet materials. If the cores were to be disposed of instead of recycled, they would create costly, both economically and environmentally, waste. Thus, the sheet material manufacturing industry is searching for a way to quickly and inexpensively clean and recycle used cores.
One common methodology employs operators, located at a core cleaning station or at the end of the manufacturing line yielding a sharp cutting blade to cut the remaining sheet material from the core. This practice is unacceptable on multiple levels. If care is not used, the sharp cutting blades will score the surface of the core, turning it into scrap. Further, there have been numerous incidents of operators injuring themselves and others with the sharp cutting blades.
Another solution is provided in U.S. Pat. No. 4,298,173. The '173 patent discloses an apparatus for unwinding a material web wherein the leading edge of the web is grabbed by nip rollers which serve to unwind the remaining web from the core as the core is being rotated. The remaining web is then disposed of for further processing and the core is sent to a core storage area. It has been observed that apparatus such as that shown in the '173 patent demand continuous operator interface to ensure the remaining material web is successfully removed from the core.
Another proposed solution for the cleaning of cores of rolls of material is provided in U.S. Pat. No. 7,717,147. The '147 patent provides an apparatus having a stripper means comprising rollers for rotating the cores and nip rollers for catching a free end of the remaining material on each used core and a pull means for pulling the remaining material off each used core. The apparatus further includes a cleaning means for cleaning the used cores after it has been treated by the stripping means and an adhesive applicator for applying adhesive to the used cores whereby the used cores are then ready for reuse as refurbished cores for new rolls of material. The '147 apparatus suffers from the same deficiency as the '173 apparatus in that it requires operator interface to ensure that the remaining material is freely and clearly cleaned off each used core.
The present invention provides an apparatus for the cleaning of used cores.
SUMMARY OF THE INVENTION
The present invention provides an apparatus for automatically removing stock remnants from unwound cores without damaging the surfaces or ends of the cores, thus providing used cores capable of reuse. The core cleaning apparatus includes a frame that carries (1) a movable cutting blade and (2) abrasion belts looped around a pair of rotatable shafts. The assembly of the rotatable shafts and belts are carried on an arm pivotally supported for movement toward a core to be cleaned to a position away from the core. When the belts are engaged to the core and moved against the exterior surface, they readily clean debris and scrap from such surface. The apparatus of the present invention can be used with the Automatic Core Cleaning Apparatus of our pending U.S. patent application Ser. No. 12/928,231 filed Dec. 7, 2010, the disclosure of which is hereby incorporated by reference. It can also be used as a stand-alone unit.
BRIEF DESCRIPT OF THE DRAWINGS
FIG. 1 is a perspective view showing the apparatus of the present invention.
FIG. 1A is an enlarged perspective view of the end portion of the assembly carrying the abrasion belts.
FIG. 2 is an elevational view of the apparatus.
FIG. 2A is an enlarged plan view of the other end of the assembly carrying the abrasion belts.
FIG. 3 is an end view of the apparatus.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings there is shown a frame 10 on which are mounted a cutter assembly 12 and a core abrasion assembly 14 .
The frame 10 includes an upper cross member 16 extending between and supported on first and second end supports 18 . The end supports 18 each include a long vertical support member 18 A a short vertical support member 18 B a horizontal support member 18 C and an angled support member 18 D extending upwardly from short support 18 B and inwardly to an engagement with the horizontal support member 18 C. The upper cross support member 16 is supported by and extends between and slightly beyond the end supports 18 . The upper cross member 16 supports a linear slide rail 20 on which the cutter assembly 12 is supported for movement between end supports 18 . The mechanism for moving the cutter assembly 12 between the end supports 18 is similar to the mechanism described in our co-pending U.S. patent application Ser. No. 12/928,231 filed Dec. 7, 2010 and forms no part of the present invention. It differs primarily in its mounting on the slide frame and the linear slide for movement relative to the core being cleaned.
The frame 10 also includes a lower support member 22 extending between end supports 18 and joined to the long vertical support members 18 A. Mounted on the lower support member 22 is a core abrasion assembly 14 mounted on the lower support member 22 by means of pillow block bearings 26 .
The core abrasion assembly 14 includes a pair of spaced apart arms 28 which support carry shaft support frames 38 . The shaft support frames 38 are engaged with the upper and lower rotatable shafts 32 about which are trained a plurality (4 as shown in FIGS. 1 and 2 ) of abrasion belts 34 . The abrasion belts 34 may be a multi-ply conveyor belt material or similar material having good wear characteristics.
As shown in FIG. 1A , rotation of the rotatable shafts 32 is effected by means of motor 36 mounted on one of the shaft support frames 38 . The motor 36 powers rotation of the upper rotatable shaft 32 to impart movement of the abrasion belts 34 about endless loops. FIG. 2A shows the mounting of the rotatable shafts 32 on bushings 33 mounted on the shaft support frame 38 .
The arms 28 are pivotally supported on the pillow block bearings 26 . Rotation of the arms 28 from the position shown in phantom lines in FIG. 3 spaced from the core C to be cleaned to the position shown in full lines engaged to the outer surface of the core C being cleaned is effected by means of a motor 42 engaged to an actuator 44 carried by mount 46 .
In operation, a core C is supported in a position for having the scrap web material cut from its exterior surface by the cutter assembly 12 as described in our co-pending application Ser. No. 12/928,231. Following such cutting operation, the motor 42 may be actuated to rotate the arms 28 and the core abrasion assembly 24 carried thereon to the position shown in full lines in FIG. 3 , at which position the abrasion belts 34 are in contact with the exterior surface with the core C. Actuation of the motor 36 imparts rotation to the upper rotatable shaft 32 thereby causing the belts 34 to move around the endless loop over the shafts 32 and to clean the core C against which the belts 34 are pressed, to thereby remove any excess debris and scrap from such surface.
This invention has been described in considerable detail with reference to its preferred embodiment. However, as indicated previously, the invention is susceptible to numerous modifications, variations, and substitutions without departure from the spirit and scope of the invention as described in the foregoing detailed description and as defined in the following appended claims.
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Apparatus for removing remnants of debris from the exterior surface of cores includes an assembly moveable from a position spaced from the exterior surface of the cores to a position adjacent the exterior surface. One or more abrasion belts are looped around rotatable shafts which move the belts to abrade the exterior surface of the cores.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to a facemask, and particularly to a sterilizing facemask that can sterilize inhaled and exhaled air bidirectionally.
BACKGROUND OF THE INVENTION
[0002] Owing to development of industries, considerable quantities of exhaust gases by industries and traffic vehicles are generated. Accordingly, in order to let people breathe fresher air, some products emerge to meet the demand. Nowadays, the filtering layers of an air purifier and facemasks used by people have the function of filtering air. The structure and design of the facemask disclosed in U.S. Pat. No. 6,520,181 emphasizes in preventing gases from leaking out without special adhesion function. The general planar foldable facemask disclosed in U.S. Pat. No. 4,941,470 only contains a layer of meltblown polypropylene fabrics without the effects of suppressing bacteria and of molecule adhesion, and thereby cannot be used in environments with high air pollution and with high bacteria pollution. The three-layer mask with activated charcoal disclosed in U.S. Pat. No. 6,070,578 has the effect of molecule adhesion but has no bacteria suppressing effect. Taiwan patent number 163,571 discloses using photocatalyzers to resist bacteria. However, the photocatalyzers tend to depart or peel off from the non-woven fabrics or textiles and to be inhaled into lungs, causing danger to people. In addition, because the photocatalyzers is on the middle layer of the facemask, it cannot absorb ultraviolet light and thereby the bacteria suppressing effect is reduced. Furthermore, the planar facemask disclosed in Taiwan patent number 154,980 has no bacteria suppressing and molecule adhesion effects.
[0003] Ordinary facemasks are designed for filtering inhaled external air, and there are plenty of materials used, for example, photocatalyzers, nanometer silver, and chitin. Nevertheless, they are single-layered, and thereby cannot filter exhaled air to avoid germs from spreading by a carrier. Photocatalyzers can be used when air comes from outside. Nevertheless, when exhaling air, one side of the facemasks contacts with skins and thereby cannot be illuminated by visible light or ultraviolet light. Hence, photocatalyzing effect is bad or even ineffective to sterilize both exhaled and inhaled air. Accordingly, the present invention provides a novel structure of facemasks for providing distinct sterilizing mechanisms on exhaled and inhaled air.
SUMMARY
[0004] The purpose of the present invention is to provide a sterilizing facemask with a multi-layer filter for providing distinct sterilizing mechanisms on exhaled and inhaled air for users, and thereby to provide a facemask with better sterilizing effects on exhaled and inhaled air.
[0005] The other purpose of the present invention is to provide a sterilizing facemask with a multi-layer filter for increasing the pressure drop inside the facemask and thereby further provide an increased respiration zone for the facemask structure.
[0006] In order to achieve the purposes and effects described above, the present invention provides a sterilizing facemask with a multi-layer filter, which discloses a first sterilizing layer and a second sterilizing layer. The first sterilizing layer uses ultraviolet light or visible light in external light for providing hydroxyl free radicals to sterilize inhaled air. Because the second sterilizing layer is inside of the facemask, there is no light provided. The second sterilizing layer inactivates the enzyme of bacteria's sulfhydryl group to sterilize exhaled air. In addition, in accordance with types of germs carried by users, the material of the second sterilizing layer can be further modified to ensure that the exhaled air is sterilized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a structural schematic diagram according to a preferred embodiment of the present invention;
[0008] FIG. 2 is a front view of a facemask with a shelter layer according to another preferred embodiment of the present invention;
[0009] FIG. 3 is a structural schematic diagram of a facemask with a function layer according to another preferred embodiment of the present invention;
[0010] FIG. 4 is a structural schematic diagram of a three-dimensional facemask with sterilizing functions according to another preferred embodiment of the present invention; and
[0011] FIG. 5 is a structural schematic diagram of a facemask with sterilizing functions according to another preferred embodiment of the present invention.
DETAILED DESCRIPTION
[0012] In order to make the structure and characteristics as well as the effectiveness of the present invention to be further understood and recognized, the detailed description of the present invention is provided as follows along with preferred embodiments and accompanying figures.
[0013] FIG. 1 is a structural schematic diagram according to a preferred embodiment of the present invention. As shown in the figure, the present invention discloses a multi-layer sterilizing facemask, which includes a first sterilizing layer 10 , a second sterilizing layer 20 . The first sterilizing layer 10 is adapted on one side of the second sterilizing layer 20 for providing better filtering effects by sterilizing inhaled and exhaled air in two distinct mechanisms. In accordance with types of germs carried by users, the material of the second sterilizing layer 20 can be further modified to sterilize the exhaled air.
[0014] Because surface electrons on the first sterilizing layer 10 can absorb sufficient energy to escape when the first sterilizing layer 10 is illuminated by external light, no matter ultraviolet light or visible light, holes will be formed on the locations from which the electrons escape. The holes will oxidize (that is, capture the electrons thereof hydroxyl group (OH—) that is ionized from neighboring water molecules and make the OH— become very active hydroxyl free radicals. When the hydroxyl free radicals meet organic materials, they will capture the electrons back, and the organic molecules will break, disintegrate, and decompose. Most of common pollutions or pathogens are carbohydrates, which will mostly become non-harmful water and carbon dioxide, and thereby the purposes of decontamination and sterilization can be achieved. The material of the first sterilizing layer 10 is chosen from the group consisting of TiO 2 , ZnO, SnO 2 , ZrO 2 , CdS, ZnS, and sulfides. Furthermore, because the second sterilizing layer 20 cannot be illuminated by visible light or ultraviolet light, the material thereof cannot be chosen as the same material as the first sterilizing layer 10 . The material of the second sterilizing layer 20 is chosen from chitin or silver ions. In addition, according to types of germs carried by users, the material of the second sterilizing layer 20 is different.
[0015] Chitin is a copious natural resource. It is manufactured using biosynthesis by one billion tons each year, and is the most abundant natural organic matter second to cellulose on earth. The structure of chitin is very similar to cellulose. It is a natural polysaccharide, and is named as (1,4)-2-acetamino-2-deoxy-β-D-glucose. Chitin has the biological functions of collagen in tissues of higher-grade animals, and of cellulose in tissues of higher-grade plants, thereby it has fine adaptation for both animals and plants. In addition, it is biologically degradable and oral non-poisonous. Thereby, nowadays, it has become a new material with wide applications. Chitosan is the product of chitin after deacetylation treatment, and is solvable in solutions with low acidity. Because it contains ionized amine group to combine with acid molecules, it has many special physical and chemical properties, as well as exceptional biological functions. Chitosan is the most important derivative of chitin and is the product of chitin after deacetylation above 70%. It is, so far, the only natural alkaline polysaccharide with the properties of non-toxicity, biological degradability, and good biological compatibility. Chitin can eliminate over 99% of pathogenic toxicity, and will not produce antibodies and cause allergic reactions. In addition, it also has the properties of moisture holding and non-toxicity.
[0016] The sterilizing mechanism of silver is when nanometer silver approaches virus, fungus, bacteria, or bacteriophage, it will cause their protein enzyme, which is responsible for oxygen metabolism, decompose and lose its effect. Hence, the virus, fungus, bacteria, or bacteriophage cannot carry out normal oxygen metabolism and thereby will die naturally.
[0017] FIG. 2 is a front view of a facemask with a shelter layer according to another preferred embodiment of the present invention. As shown in the figure, the present invention further installs a shelter layer 30 between the first sterilizing layer and the second sterilizing layer. The material thereof can be chosen from damp-proof materials or water-repellent materials. A plurality of holes 32 is adapted outside of the shelter layer 30 for providing visible light or ultraviolet light.
[0018] FIG. 3 is a structural schematic diagram of a facemask with a function layer according to another preferred embodiment of the present invention. As shown in the figure, the present invention further includes an odor-removal layer 40 , an electrostatic layer 50 , and a skin contact layer 60 . The odor-removal layer 40 and the electrostatic layer 50 are adapted between the first sterilizing layer 10 and the second sterilizing layer 20 ; the order of the odor-removal layer 40 and the electrostatic layer 50 can be swapped. In addition, the odor-removal layer 40 can be made of activated charcoal; the skin contact layer 60 is adapted inside of the second sterilizing layer 20 .
[0019] FIG. 4 is a structural schematic diagram of a three-dimensional facemask with sterilizing functions according to another preferred embodiment of the present invention. As shown in the figure, the facemask constructed by the first sterilizing layer and the second sterilizing layer according to the present invention includes an upper surface 2 , which is located at the upper part of the facemask, a center surface 4 , which is located at the center of the facemask and below the upper surface, and a lower surface 6 , which is located at the lower part of the facemask and is below the center surface 4 . The upper, center, and the lower surfaces form an integral unit of surface. First, fold inwardly the upper surface 2 and the lower surface 6 besides the center surface 4 , respectively. When using the facemask, the upper surface 2 and the lower surface 6 can extend to support the center surface 4 and to form a sterilizing facemask.
[0020] FIG. 5 is a structural schematic diagram according to another preferred embodiment of the present invention. As shown in the FIG. 5 , the present invention discloses a multi-layer sterilizing facemask, which comprises a first sterilizing layer 10 and a second sterilizing layer 20 , which adapted inside of the first sterilizing layer 10 . The first sterilizing layer 10 and the second sterilizing layer 20 is applied for sterilizing inhaled external air and exhaled internal air from human bodies respectively. Likewise, the present invention further includes a decelerating layer 70 adapted between the first sterilizing layer 10 and the second sterilizing layer 20 . The decelerating layer 70 is utilized for extended the sterilizing effect to improve the sterilizing effect, whereby it should be made the inhaled external air and the exhaled internal air from human bodies both slow down to pass through the multi-layer sterilizing facemask. Moreover, the deceleration layer 70 further includes a electrostatic layer 80 , which make the sterilizing effect better, even more. Hence, the present invention should let people live better, whereby it is sterilizing the inhaled external air and the exhaled internal air from human bodies.
[0021] Accordingly, the present invention conforms to the legal requirements owing to its novelty, unobviousness, and utility. However, the foregoing description is only a preferred embodiment of the present invention, not used to limit the scope and range of the present invention. Those equivalent changes or modifications made according to the shape, structure, feature, or spirit described in the claims of the present invention are included in the appended claims of the present invention.
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A sterilizing facemask with a multi-layer filter discloses a first sterilizing layer and a second sterilizing layer. The first sterilizing layer provides inhaled aseptic air such as using ultraviolet light or visible light in external light hydroxyl free radicals to sterilize. The second sterilizing layer provides exhaled aseptic air from human such as using inactivated the enzyme of bacteria's sulfhydryl group to sterilize. In addition, in accordance with types of germs carried by users, the material of the second sterilizing layer can be further modified to ensure that the exhaled air is sterilized.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to provisional application Ser. No. 61/496,835, filed Jun. 14, 2011.
FIELD OF THE DISCLOSURE
This disclosure relates in general to well drilling and in particular to a shear ram assembly for a blowout preventer (“BOP”) that has guide arms to move a well pipe away from a side wall of the bore of the shear ram assembly during shearing.
BACKGROUND OF THE DISCLOSURE
Offshore drilling rigs normally employ a riser to connect the subsea wellhead with the drilling rig. A blowout preventer is located at a lower end of the riser. Land rigs also use blowout preventers. A blowout preventer is a large assembly having many features for closing the riser in the event high pressure in the wellbore begins pushing the drilling mud upward. Those features include an annular blowout preventer that seals around pipe regardless of the diameter. The blowout preventer also has pipe rams that are sized to close and seal around pipe strings of certain diameters. The blowout preventer also has shear rams that will shear a drill pipe string or a production tubing string in the event of an emergency.
Pipe shear rams have two rams, each of which has a blade mounted to it. Pistons move the rams toward each other to shear pipe extending through the blowout preventer. One blade is located at a higher elevation than the other and slides over the lower one when the shear rams close. Often the pipe string will be off-centered relative to the axis of the bore extending through the shear ram assembly. The blades have converging side portions that lead to a central area for centering the pipe as the rams close. In some pipe ram assemblies, a remote possibility exists that the pipe string will remain at an outside wall of the bore during closure, which could lead to incomplete shearing of the pipe string.
SUMMARY
The pipe shear ram assembly has a housing with a bore extending vertically for the passage of a pipe string. The assembly has first and second ram blocks, each having a blade, the blades being positioned such that one slides over the other when the first and second ram blocks are moved forward to a closed position. Two guide arms protrude from the first ram block toward the second ram block. Each of the guide arms has a tip and a wedge surface on an inboard side extending rearward from the tip. The wedge surfaces are farther apart from each other than the blade and guide the pipe string toward an axis of the bore in the event the first and second ram blocks are moved to the closed position.
In one embodiment, a rearward edge of each of the wedge surfaces is located substantially the same distance forward of a face of the first ram block as an upper edge of an outboard end of the blade of the first ram block. Preferably each of the wedge surfaces is located in a vertical plane. A distance between rearward ends of the wedge surfaces is less than a diameter of the bore in one embodiment. Each of the wedge surfaces may be flat.
Each of the blades may have a length between outboard ends that is less than a diameter of the bore. A pair of recesses are located on the second ram block adjacent opposite ends of the blade of the second ram block for receiving the guide arms when the first and second ram blocks move to the closed position. Each of the recesses has an upper wall. The guide arms are mounted to the first ram block so as to avoid sliding contact with the upper walls as the ram blocks move to the closed position. The bottoms and outboard sides of the recesses may be open. In one embodiment, the blade of the first ram block slides over the blade of the second ram block when in the closed position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the ram blocks of a shear ram assembly in accordance with this disclosure.
FIG. 2 is a side view of the ram blocks of FIG. 1 .
FIG. 3 is a top view of the ram blocks of FIG. 1 .
FIG. 4 is a bottom perspective view of the ram blocks of FIG. 1 .
FIG. 5 is a front view of the upper ram block of FIG. 1 .
FIG. 6 is a top view of the blades and guide arms of the ram blocks of FIG. 1 , shown in an open position.
FIG. 7 is a top view of the blades and guide arms of FIG. 6 , shown in a partially closed position.
FIG. 8 is a perspective view of the ram blocks of FIG. 1 installed within a subsea blowout preventer assembly.
DETAILED DESCRIPTION
Referring to FIG. 1 , shear rams 11 are shown removed from the housing or bonnet in which they are located. Shear rams 11 are part of a ram BOP assembly that is part of a stack assembly. In the case of offshore drilling, the stack assembly is located at the lower end of a riser extending downward from a drilling vessel. The lower end of the BOP stack assembly secures to a subsea wellhead on the sea floor. The BOP stack assembly will normally also contain pipe rams, variable bore rams, and a quick disconnect mechanism for disconnecting from the riser in the event of an emergency. When actuated, shear rams 11 will close the through bore and also shear pipe in the well, such as drill pipe, tubing, or casing.
Shear rams 11 include an upper ram assembly 13 having a face or forward end 15 . A semi-circular seal groove 16 is located on the upper side of upper ram block 13 for receiving a portion of an elastomeric seal. An upper shearing blade 17 mounts to forward end 15 . Upper blade 17 has a forward face 23 with an upper edge 19 and a lower edge 21 . Lower edge 21 extends forward farther from forward end 15 than upper edge 19 in this example, resulting in face 23 inclining relative to vertical. Face 23 is also generally concave or converging, resulting in the center of face 23 between its outboard ends 24 being recessed relative to the more forward portions of face 23 at outboard ends 24 . A variety of different shapes for upper blade 17 may be employed.
Pipe guide arms 25 are located on the outboard sides of upper ram block forward end 15 . Each arm 25 could be formed integrally with upper ram block 13 , or they could be otherwise attached, such as by welding or fasteners. Each arm 25 has a vertically oriented inboard side 27 extending forward from a base 37 of each arm 25 . Base 37 is designated to be where arm 25 joins forward end 15 . Also each arm 25 has a forward end or tip 29 . A wedge surface 31 extends from a junction with a forward end of inboard side 27 to tip 29 . Each inboard side 27 is parallel with a longitudinal axis 28 of shear rams 11 in this example. Wedge surface 31 may be a flat vertical surface, as shown, that is at an acute angle relative to longitudinal axis 28 . In this embodiment, wedge surface 31 is at an angle of about 30 degrees relative to longitudinal axis 28 and to inboard side 27 . Rather than flat, wedge surface 31 could be a curved surface. Each guide arm 25 has an upper side 33 that is flat and in a horizontal plane in this example. A chamfer or bevel 34 optionally may be at the intersection of upper side 33 with tip 29 .
As shown in FIG. 2 , upper side 33 is spaced at a lower elevation on upper ram block forward end 15 than upper blade lower edge 21 . Upper side 33 is not located directly under upper blade 17 in this example because inboard side 27 of each arm 25 is approximately the same outboard distance as one of the upper blade outboard ends 24 , as shown in FIG. 3 . Also, FIGS. 2 and 3 illustrate that tip 29 extends forwardly more than upper blade 17 from forward end 15 . The junction of inboard side 27 with wedge surface 31 is approximately in vertical alignment with the junction of upper shear blade upper edge 19 and outboard end 24 . Wedge surface 31 joins inboard side 27 approximately the same distance from upper ram block forward end 15 as the distance from forward end 15 to the upper edge 19 of upper blade face 23 at outboard end 24 .
Each guide atm 25 has an outboard side 35 that extends from arm base 37 to tip 29 . Outboard side 35 may be at an acute angle relative to longitudinal axis 28 . In this embodiment, the acute angle is about 15 degrees relative to longitudinal axis. Tip 29 has a smaller height and width than base 37 .
FIG. 4 shows a lower side 39 of each arm 25 . Lower side 39 is shown as being flat and in a plane parallel with upper side 33 ( FIG. 3 ). A beveled surface 41 may join an outboard edge of lower side 39 with outboard side 35 . Beveled surface 41 is shown to be in a plane inclined relative to horizontal.
Referring still to FIG. 4 , and also to FIG. 5 , the lower side of upper ram block 13 has a sheared pipe end recess 43 . Recess 43 has a rear wall portion 45 that joins side wall portions 47 . Wall portions 45 and 47 are vertical walls positioned to receive the upper end of a well pipe after it has been sheared. Rearward wall portion 45 is illustrated as being partially cylindrical and blends with side wall portions 47 , which are straight. Other shapes for shear pipe end recess 43 are feasible. FIG. 4 also illustrates a T-shaped connector slot 49 on the rearward end of upper ram block 13 for connecting to a piston rod.
Referring again to FIG. 1 , a lower ram block 51 is illustrated in horizontal alignment with upper ram block 13 . Lower ram block 51 has a forward end 53 that is parallel to forward end 15 of upper ram block 13 . A top seal groove 55 in the upper side of lower ram block 51 receives an elastomeric seal and aligns with seal groove 16 to form a continuous seal when ram blocks 13 , 51 are in abutment with each other. The seal is not necessarily circular. Lower ram block 51 has a sheared pipe end recess 57 for receiving the lower end of well pipe after shearing. Sheared pipe end recess 57 has a curved rear wall portion 59 that blends with two straight side wall portions 61 . Other shapes are feasible.
A lower blade 63 attaches to forward end 53 of lower ram block 51 . Lower blade 63 is at a lower elevation than upper blade 17 , as illustrated in FIG. 2 . Lower blade 63 slides under upper blade 17 when shearing. An upper edge 65 of lower blade 63 is at a slightly lower elevation than lower edge 21 of upper blade 17 . Lower blade 63 has a lower edge 67 that is closer to lower block forward end 53 than the upper edge 65 . A face 69 extends between lower edge 67 and upper edge 65 and is thus inclined relative to vertical. As illustrated in FIG. 2 , in this example, the inclination of lower blade face 69 is the same as the inclination of upper blade face 23 . Lower blade face 69 also recesses or converges to a central area that is closer to lower block forward end 53 than the outboard ends 70 of lower blade 63 , as shown in FIGS. 1 and 3 . The length of lower blade 63 from one outboard end 70 to the other is the same as the length of upper blade 17 from one outboard end 24 to the other.
Referring to FIG. 4 , which shows the bottom of lower block 51 , a recess 71 is located on lower shear block 51 along each outboard side outward and rearward from lower blade outboard ends 70 . Each recess 71 comprises a space or clearance provided along an outboard side to receive one of the arms 25 when ram blocks 13 , 51 are closed. Each recess 71 is defined by a downward-facing upper side wall 72 and an inboard side wall 74 , side walls 72 and 74 being flat and perpendicular in this example. Each recess 71 is aligned with one of the arms 25 to receive the arm when in the closed or sheared position. Each recess 71 has a greater longitudinal length than the length of each arm 25 . Also, upper side wall 72 has a greater width than each arm 25 , and inboard side wall 74 has a greater height than the height of each arm 25 from its lower side 39 to its upper side 33 ( FIG. 2 ). Recess 71 is not a closed cavity as it has no outboard side wall or bottom side wall. There is no interference between upper side wall 72 and upper side 33 ( FIG. 2 ) of arm 25 . There is no interference between inboard side 27 of arm 25 and inboard side wall 74 . Arm upper side 33 could optionally slidingly engage recess upper side wall 74 , but preferably no significant vertical forces would be created on lower ram block 51 as a result.
A vertical center point of each arm 25 is approximately the same as a vertical center of lower blade 63 . When moving to the closed or sheared position, lower blade 63 will slide between the two arms 25 as the arms enter recesses 71 . The outboard ends 70 of lower blade 63 will be closely spaced from the inboard sides 27 of arms 25 as the arms enter recesses 71 . A T-shaped connector slot 76 for connection to a piston rod is located on the rearward end of lower block 51 .
Referring to FIGS. 6 and 7 , a housing or bonnet 73 for shear rams 11 is illustrated schematically by dotted lines. Shear ram blocks 13 , 51 (only a portion shown) are mounted in bonnet 73 and move toward and away from each other along axis 28 by pistons not shown). A vertical opening or bore 75 extends through bonnet 73 . The lengths of blades 17 , 63 are somewhat less than the diameter of bore 75 . The distance between arm tips 29 , measured from the inside surface of each arm tip 29 , is approximately the diameter of bore 75 . Stated another way, the distance between wedge surfaces 31 , measured at the forward ends of wedge surfaces 31 , is approximately the diameter of bore 75 . The distance between the rearward ends of wedge surfaces 31 , is approximately the same as the length of blade 17 and less than the diameter of bore 75 . Bore 75 has the same diameter as the riser pipe (not shown) attached to bonnet 73 for receiving well pipe 77 extending from the vessel into the wellbore.
Well pipe 77 may be of various diameters depending on the purpose and type of the pipe. Well pipe 77 could coincide with bore axis 79 or be offset to one side as illustrated. A side of well pipe 77 could be touching a side portion of bore 75 , particularly if buckling of well pipe 77 has occurred in the wellbore.
FIG. 6 shows shear rain blocks 13 , 51 fully open. While fully open, no portion of blades 17 , 63 or arms 25 will protrude into bore 75 . FIG. 7 shows shear ram blocks 13 , 51 in the process of being closed to shear pipe 77 . As blades 17 , 63 advance into bore 75 , the guide arms 25 contact well pipe 77 and help pipe 77 to move towards bore axis 79 . The wedge surfaces 31 makes sure that any part of well pipe 77 placed anywhere in bore 75 can be brought within range of the shear blades to be completely sheared. The full diameter of well pipe 77 will be contacted by blades 17 and 63 . When blade 17 is located midway across bore 75 , there will be no large gap between outboard ends 24 of blade 17 and the sides of bore 75 as the gaps will be filled by arms 25 .
The shear ram assembly 11 as described will shear a pipe string 77 when closed, even if the pipe string 77 is initially located against an outside wall of the housing bore 75 . The pipe string 77 will not be pushed outward to a position resulting in an incomplete shearing. The guide arms 25 provide two functions. The first is to push or direct the pipe string 77 toward the center of the bore 75 . The second is to remove or support the side load on the cutting blade 77 when the pipe string 77 is off center.
FIG. 8 shows blind shear rams 11 installed within a typical subsea blowout preventer assembly. The blowout preventer assembly has a blowout preventer (“BOP”) stack 81 that includes a frame with a wellhead connector 85 at the lower end for connecting to a subsea wellhead assembly (not shown). Blind shear rams 11 are normally located above pipe rams, which in this example includes pipe rams 91 , 93 , and 95 . Each pipe ram 91 , 93 and 95 has rams with semi-cylindrical recesses on the mating faces for closing around a different size range of pipe. When closed, blind shear rams 11 will seal off the bore and if pipe is present, will shear the pipe.
A lower marine riser package (LMRP) 94 connects to the upper end of BOP stack 81 . An annular BOP 95 may be located at the lower end of LMRP 94 . Annular BOP 95 will close around any size of pipe and seal the annulus between the pipe and the side wall of the bore. Annular BOP 95 will also seal fully even if a pipe is not present. A flex joint 97 is located at the upper end of LMRP 94 to allow flexing of a lower end of a riser string 99 connected to flex joint 97 . Choke and kill lines 101 extend from below annular blowout preventer 95 to alongside riser 99 for pumping fluid into the well. In the event of an emergency, LMRP 94 and riser 99 can be detached from BOP stack 81 . Redundant control pods 103 mount to LMRP 94 and contain hydraulic and electrical circuitry for controlling movement of the various rams 11 , 81 , 91 and 93 annular BOP 95 and other equipment. Control pods 103 are retrievable from LMRP 94 and are connected to an umbilical (not shown) leading to the drilling vessel at the surface.
While the shear ram assembly has been shown in only one of its forms, it should be apparent to those skilled in the art that it is not so limited but is susceptible to various changes without departing from the scope of the disclosure.
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A pipe shear ram assembly has a housing having a bore extending vertically therethrough for the passage of a pipe string. Ram blocks have blades positioned such that one slides over the other when the first and second ram blocks are moved toward each other to shear a well pipe. A pair of guide arms extend from one of the rams. The guide arms have tips protruding a greater distance than the blade. Each of the guide arms has an inboard wedge surface beginning at the tip and extending along a line that intersects the longitudinal axis for guiding the pipe string toward a bore axis of the bore in the event the first and second ram blocks are moved to the closed position.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application of U.S. application Ser. No. 11/673,737 filed Feb. 12, 2007, incorporated by reference herein and for which benefit of the priority date is hereby claimed. application Ser. No. 11/673,737 is a divisional application of U.S. application Ser. No. 11/255,565 filed Oct. 21, 2005, incorporated by reference herein and for which benefit of the priority date is hereby claimed. application Ser. No. 11/255,565 is a continuation of Ser. No. 11/007,968 filed Dec. 9, 2004, which claims priority from U.S. provisional patent application Ser. No. 60/529,457, filed Dec. 12, 2003, by Alan Corbett Ferguson, incorporated by reference herein and for which benefit of the priority date is hereby claimed.
TECHNICAL FIELD
[0002] The present invention relates to dry-stack concrete masonry systems for building structural load bearing and non-load bearing walls and, more particularly, two distinct concrete masonry units with a web offset lug design that provides for both stack bonding and running bond construction with unobstructed vertical cell alignment to facilitate both solid and partial concrete grouting (for structural strength} with and without steel reinforcement.
BACKGROUND INFORMATION
[0003] An advantage of dry stack masonry systems is that the labor component of installation can be dramatically reduced. Some studies have shown that dry stack masonry systems are up to ten times faster to install than conventional joint mortared masonry systems. Because these systems do not use bonding mortar to provide joint support, it may be necessary to use other means of developing wall strength.
[0004] One technique to develop wall strength is to pour wet concrete or grout into the openings of the block to form vertical posts. The wet concrete is poured into the open cells of the concrete block. Various building codes may require dry-stacked concrete block cells to be filled differently in order to provide specified structural integrity. Some applications may require all the cells to be filled with concrete. Other applications may require the concrete to be poured into distinct vertical columns and only in certain cells or cores of the block. These applications may require cells, for example, to be filled generally at four foot on center increments and/or at wall corners and jambs of windows and doors or various load points. A general overview of the use of current dry stack methods in masonry wall construction can be found in National Concrete Masonry Association's (NCMA) technical publication TEK 14-22 “Design and Construction of Dry-Stack Masonry Walls.”
[0005] The vertical posts are typically reinforced with reinforcement members, for example, steel rebar. The problem with many dry stack block systems is that when stacked, the cells or core holes of the block are not completely aligned. The cells between successive layers of block may vary in size as shown in FIGS. 1A and 1B . FIGS. 1A and 1B show a stack of a conventional dry block system 100 . The middle row 102 provides a narrow passage 104 relative to the top row 106 and bottom row 108 . When concrete is poured in the cells the variation in cell dimensions may hinder or prevent reinforcement members from being inserted in the cores to form the vertical posts. In addition, the variation in cell dimensions may make it difficult to fill the voids within the cell. Many conventional dry stack block systems may provide little or no damming capacity when filling the cells of a dry stack block wall structure.
[0006] The current dry stack wall systems used in building construction for load bearing and non-load bearing walls that incorporate raised lugs for alignment and interlocking do not provide adequate or uniform core orientation, as previously discussed. Additional descriptions of prior art raised lug systems are disclosed in U.S. Pat. No. 3,968,615 to Ivany, U.S. Pat. No. 4,182,089 to Cook, and U.S. Pat. No. 4,640,071 to Haener.
[0007] When stacked in a running bond, a core block resting on top of two halves of a lower adjacent block, the lack of uniform orientation of prior art systems fail to provide a uniform and well-aligned core for forming concrete posts. The prior art dry-stack block systems require lugs that project above the top surface of the block. These lugs tend to limit where blocks can be stacked in relation to one another. In addition, the prior art alignment of lugs prevents the stacking of blocks in a single stack bonded configuration (one block resting completely on top of a lower adjacent block).
SUMMARY
[0008] In one aspect the invention features a dry stack building block for constructing a masonry wall. The block may have a front section having an outer surface, an inner surface, a bottom surface, and a top surface. The block may also have a rear section substantially parallel to the front section having an outer surface, an inner surface, a bottom surface, and a top surface. Two or more webs may couple the inner surface of the front section to the inner surface of the rear section and having a top surface and a bottom surface. Two or more pairs of lugs may extend above the top surface of the front section and the top surface of the rear section. Each pair of lugs may have a first lug offset from a second lug in an axis running parallel to the top surfaces of the front section and the back section and perpendicular to the inner surfaces of the front section and the back section.
[0009] Embodiments may include one or more of the following. One pair of the two or more pairs of lugs may be positioned to receive a second duplicate dry stack block staged halfway off-center and a second pair of the two or more lugs may be positioned to receive a third duplicate dry stack block staged halfway off-center in a direction opposite and adjacent to the second stack block. The top surfaces of the front section and rear section may be adapted to receive a bottom surface of a front section and a bottom surface of a rear section of another duplicate dry stack building block. The outer surface of the front section and the outer surface of the rear section may have a chamfered edge. A first lug of each pair of the two or more pairs of lugs may have a chamfered edge adjacent to the front section and the second lug of each pair of the two or more pairs has a beveled edge adjacent to the rear section. The two or more webs may be substantially perpendicular to the front section and the rear section. Each of the two or more webs may have one lug of a pair of the two or more pairs of lugs adjacent to the inner surface of the front section and a first side surface of the web and a second lug of the pair adjacent to the inner surface of the rear section and a second side surface opposite the first side surface of the web. A first angle produced by a first web of the two or more webs and the front section plus a second angle produced by a second web of the two or more webs and the front section may be substantially equal to 180 degrees. Each of the two or more webs may have one lug of a pair of the two or more pairs of lugs extending from the top surface of the web and adjacent to the front section and a second lug of the pair extending from the top surface of the web and adjacent to the rear section. The two or more webs may have a knock-out portion for providing a bond beam.
[0010] In another aspect the invention may feature a corner block for constructing a corner wall portion. The corner block may have a front section having an outer surface, an inner surface, a bottom surface, and a top surface. The corner block may also have a rear section substantially parallel to the front section having an outer surface, an inner surface, a bottom surface, and a top surface. A side section may be coupled and substantially perpendicular to the front section and the back section. The side section may have an outer surface contacting the outer surfaces of the front section and rear section, a bottom surface, and a top surface. The corner block may have one or more webs coupling the inner surface of the front section to the inner surface of the rear section and spaced to receive the one or more pairs of lugs.
[0011] Embodiments of the invention may have one or more of the following advantages. The invention may provide an improved dry-stack concrete masonry block for constructing masonry load, bearing and non-load bearing wall assemblies. The invention may allow for improved core alignment from the bottom to the top of wall construction. The invention may also make partial filling of dry-stack block cells faster, easier, and stronger. The invention may also make structural reinforcement of wall assembly easier and faster in conjunction with concrete or without concrete (i.e. post tensioned). The invention may also allow the installer to construct in both running bonded and stack bonded orientations.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] These and other features and advantages of the present invention will be better understood by reading the following detailed description, taken together with the drawings wherein:
[0013] FIG. 1A is a top plane view and FIG. 1B is a front cross sectional side view of a prior art conventional dry stack block assembled into a linear wall structure.
[0014] FIGS. 2A, 2B , and 2 C are views of the present invention comprising two dry-stack units, a stretcher unit and a corner unit shown here assembled into a wall structure turning a 90 degree corner according to an exemplary pin embodiment.
[0015] FIG. 3 is a perspective view of present invention comprising the two dry-stack units, the stretcher unit and the corner unit shown here assembled into a linear wall structure according to the exemplary pin embodiment.
[0016] FIG. 4A is a top plane view and FIG. 4B is a side profile view of the stretcher unit according to an exemplary embodiment of the invention with webs at non-right angles.
[0017] FIG. 5A is a top plane view and FIG. 5B is a side profile view of the stretcher unit according to an exemplary embodiment of the invention with webs at right angle.
[0018] FIG. 6A is a top plane view; FIG. 6B is a cross sectional view; FIG. 6C is a front profile view; and FIG. 6 d is a side profile view of the stretcher unit according to an exemplary edge-grinding and exemplary pin embodiment.
[0019] FIG. 7A is a top plane view; FIG. 7B is a front profile view; and FIG. 7C is a side profile view of the corner unit according to an exemplary pin embodiment.
[0020] FIG. 8A is a top plane view and FIG. 8B is a front cross sectional side view of the stretcher unit assembled into a linear wall structure.
[0021] FIG. 9 is a perspective view of the stretcher units stack-bonded construction.
[0022] FIG. 10A is a top plane view; FIG. 10B is a cross sectional view; FIG. 10C is a front profile view; and FIG. 10 d is a side profile view of the stretcher unit according to an exemplary chamfered edge embodiment with precision ground top and recessed lug edge.
[0023] For purposes of clarity and brevity, like elements and components will bear the same designations and numbering throughout the figures.
DETAILED DESCRIPTION
[0024] A corner wall structure 200 may use a stretcher unit 202 and a corner unit 204 to construct the corner and straight portions of a wall, as shown in FIGS. 2A, 2B , and 2 C. The stretcher units 202 have lugs 206 that extend above the top of the stretcher unit 202 . The next course of stretcher units is placed on top of the previous layer of stretcher units. The lugs 206 of the previous layer of stretcher units extend into the cells of the next course of stretcher units. The lugs provide face shell alignment, lateral strength, and lock together successive layers of units.
[0025] The stretcher units 202 have a front section and a rear section. One or more webs or ribs couple the front section to the rear section. The one or more webs may extend just below the top surface of the stretcher unit 202 or may extend all the way to the top surface of the stretcher unit 202 . The stretcher units 202 also have lugs that extend above the top surface of the stretcher unit 202 . The stretcher unit 202 and other exemplary embodiments of the stretcher unit 202 will be described in greater detail later herein. The corner units 204 may also have a front section, rear section, and one or more webs coupling the front section and rear section. The corner unit also has a side section. The side section provides a ninety-degree corner in the wall. The corner unit 204 provides a uniform surface at the corner of the wall. The corner units 204 are staggered with each successive row. The corner unit 204 and other exemplary embodiments of the stretcher unit 202 will be described in greater detail later herein.
[0026] The corner unit 204 may not have lugs extending from the top. Deformable pegs 208 in peg holes 210 may be used to position the corner unit 204 during construction. The deformable pegs 208 may be made of, for example, copper tubing. The exemplary dimensions of the copper tubing may be about 4 inch diameter with length of about one inch. The copper tubing allows the peg 208 to deform with relative little force and remain in the deformed shaped. The distorted shape of the deformable peg 208 holds the units in a plumb and square position during construction phase. The deformable pegs 208 , are not limited to a metal tubing. The deformable peg 208 may be made from a variety of materials that sufficiently lack memory and provide desired strength, for example, metals, metal alloys, composites, plastics, and polymers. The deformable pegs 208 are not limited to a tubular structure. The deformable peg 208 may be, for example, solid, a variety of cross-sectional shapes, and/or a variety dimensions.
[0027] Referring to FIG. 7 , a top receiving hole 710 and a bottom receiving hole 712 may provided prior to stacking of the units. The deformable peg 208 is position within one of the top or bottom receiving holes 710 , 712 . For example, the deformable peg 208 may be positioned with the top receiving hole 712 after the respective unit has been positioned. The top and bottom receiving holes 710 , 712 may be sized to provide a frictional fit. This allows for the depth of the receiving holes 710 , 712 to be greater than an insertion length of the deformable peg 208 . The deformable peg 208 may be position within a receiving hole 710 , 712 and lightly hammered or pressed, for example by thumb pressure, into the desired length, for example half way into the top receiving hole 710 allowing the other half to extend above the surface of the block unit to receive the bottom receiving hole 712 on the next successive unit.
[0028] The next successive unit is positioned so that the deformable peg 208 aligns with the bottom receive hole 712 . The top and bottom receiving holes 710 , 712 may be construction in a variety of methods. For example, the receiving holes 710 , 712 may be molded or punched in the block unit prior to curing, the receiving holes 710 , 712 may be drilled into the block unit on-site, or a combination of construction. For example, the top receiving hole 712 may be punched in the unit prior to curing and the bottom receiving hole 710 may be drilled. The positioning of the receiving holes 710 , 712 may be dependent on the number of pegs per block unit, the overall wall construction shape (i.e. 90 degree corner, 45 degree corner, or end of a wall), and other construction aspects.
[0029] Once the unit is maneuvered in place, the unit may be position for greater accuracy by tapping the unit with a mallet or other tool. The positioning may be accomplished immediately after place of the unit or after successive layers of units have been positioned. The positioning by tapping the unit causes the deformable peg 208 to bend or deform into a new semi angled shape. The new shape aids in holding the units in a correct position or place until concrete secures the wall permanently. The deformable peg may allow for multiple positioning. For example a unit may be tapped successively throughout the dry stacking process of the wall in order to adjust positioning of the wall. The deformable pegs 208 may be used for corners or other portions of the wall in which additional adjustment may be beneficial.
[0030] The corner unit 204 may not have lugs extending from the top. The corner unit may be used in a straight wall portion, as shown in FIG. 3 . The spacing and alignment of lugs, as will be discussed later herein, allows the corner section to be placed within a straight portion of the wall. The lugs of the lower stretcher units 202 extend into the cells of the corner unit 204 without interfering with the side section or the webs of the corner unit.
[0031] FIG. 4A is a top plane view and FIG. 4B is a side profile view of a stretcher unit 400 according to an exemplary embodiment of the invention with webs at non-right angles. The stretcher unit 400 may have a height of eight inches and a length of sixteen inches. The stretcher unit 400 has a front section 402 and a rear section 404 . The front section 402 and the rear section 404 may have a thickness of one and quarter (±) inches. One or more webs 406 couple the front section 402 to the rear section 404 . The webs 406 may have a thickness of one and a half inches (±). The webs 406 , according to this embodiment, are symmetrically angled between the front section 402 and the rear section 404 . Each web 406 has a pair of lugs 408 extending from the top surface of the web. The lugs 408 may extend above the top surface by ⅜ th (±) of an inch. The lugs may have a width and thickness of one inch (±). The angled webs 406 allow the stretcher units to be stacked in a staggered fashion without the lugs interfering with the web of a successive layer of stretcher units. The web of the successive layer of stretcher units straddles each pair of lugs 408 . The stretcher unit is supported in the lateral direction by a lug positioned between the inner surface of the front or rear section and the web.
[0032] The exemplary embodiments shown in FIGS. 4A and 4B may also include round lugs. The lugs have a round top portion, which aids in the stacking of successive stretcher units. The weight of successive stretcher units pushing down centers the unit into the correct resting position. The rounded lugs help to prevent successive stretcher units becoming stuck or partially resting on the lug of lower stretcher units. The exemplary embodiments shown in FIG. 4B may also include a knock-out portion 410 for producing a bonding-beam portion in the constructed wall. The knock-out portion 410 may extend down three inches (±) from the top surface. The knock-out portion 410 may have a three quarter inch slot to allow for placing reinforcement members or removing the knock-out portion 410 . Bonding-beams are horizontal reinforcements in the wall that add strength between the vertical columns of the constructed wall. A row of stretcher units in a wall of individual or successive rows may be designated for a bonding-beam. During construction the knock-out portion 410 may be removed to allow reinforcement members and/or poured concrete to fill the cells of a row of stretcher units. The knock-out portion 410 may be molded into the stretcher unit between the lugs 408 of the web 406 .
[0033] The exemplary embodiments shown in FIGS. 4A and 4B may also include chamfered edges on the sides for the front section and the rear section. The chamfer allows the adjacent stretcher unit to fit snuggly against the neighboring stretcher unit. The chamfers of neighboring stretcher units overlap providing additional strength and preventing leaking of concrete from the cell columns during pouring. The chamfers may have a ⅜ th (±) inch inset. The exemplary embodiments shown in FIGS. 4A and 4B may also include beveled edges on the outer surface of the front section and the rear section. The beveled edges of the stretcher unit give the wall a more traditional block construction look. The beveled edge outlines the profile of the block without the need for grouted joints. The edge is not limited to a bevel. The edge may have a chamfer or other profile to outline the block face.
[0034] An exemplary embodiment of the invention with webs at right angles is shown in FIG. 5A and FIG. 5B . The stretcher unit 500 has a front section 502 and a rear section 504 . One or more webs 506 couple the front section 502 to the rear section 504 . The webs 506 , according to this embodiment, run perpendicular between the front section 502 and the rear section 504 . The webs 506 may be spaced four inches (±) from the end of the stretcher unit 500 . To provide cores that line up, each web 506 has a pair of alternating, adjacent lugs 508 . The lugs 508 extend above the surface of the stretcher unit 500 and allow the stretcher units to be stacked in a staggered fashion without the lugs 508 interfering with the web of a successive layer of stretcher units.
[0035] A first lug of the pair of lugs is coupled against a first surface of a first web and an inner surface of the rear section. A second lug of the pair of lugs is coupled against a second surface of the first web and the inner surface of the front section. A second pair of lugs for the stretcher unit has a first lug of the second pair coupled against a first surface of a second web and an inner surface of the front section. A second lug of the second pair of lugs is coupled against a second surface of the second web and the inner surface of the rear section. Each of the lugs in the first pair of lugs is positioned on alternating sides of the first web. Each lug of the second pair of lugs is also positioned on alternating sides of the second web; however, the lugs are on opposite sides from the first web. This allows the successive layer of stretcher units to rest on the stretcher unit and allows the lugs 508 of the stretcher unit 500 to protrude into the cells of the successive layer of stretcher units without interfering with the lugs of the successive layer of stretcher units.
[0036] When the wall is constructed the stretcher units may be staged half way off-center for each successive row. This allows the alternating pairs of lugs to straddle the webs of successive rows of stretcher units. The stretcher unit 500 is supported in the lateral direction by a lug positioned between the inner surface of the front or rear section and the web. The constructed wall locks together by the protruding lugs extending into the cells and straddling the webs of successive rows of stretcher units above and below the stretcher unit.
[0037] The stretcher unit 500 may also have a beveled profile on the outer surface of the front section and rear section. The stretcher unit 500 may also have a chamfered side edge for coupling to adjacent units. In addition, the stretcher unit may have a knock-out portion for producing a bonding-beam. These features are similar to those previously described herein with respect to the exemplary embodiment disclosing the exemplary stretcher unit 400 with angled webs.
[0038] An exemplary embodiment of the invention with beveled lug profiles is shown in FIGS. 6A, 6B , 6 C, and 6 D. The exemplary embodiments 600 may include a beveled lug profile 602 . The lugs 604 have a beveled surface adjacent to the outer surface of the front section 606 and the rear section 608 . The beveled profile aids in the stacking of successive stretcher units. The weight of successive stretcher units pushing down centers the unit into the correct resting position. The beveled lug profiles 602 help to prevent successive stretcher units from becoming stuck or partially resting on the lug of lower stretcher units. In addition to a beveled profile on the surface of the lug facing the outer surface of the front section and the rear section, the lugs may also have a beveled surface adjacent to the web (not shown in Figures). The additional beveled profile aids in stacking and aligning the face shells of the stretcher unit as previously discussed.
[0039] A top surface 610 of front section 606 and the rear section 608 may be grinded to provide a greater degree of accuracy in of the height for the stretcher unit. This greater degree of accuracy may be used to allow for dry stacking the units without the need for shims or leveling supports. The units may be molded using convention block molding techniques. The grinding is preformed after curing. As will be discussed later herein, the lugs 604 may have a recess to provide better alignment. The top surfaces 610 of the front section 606 and rear section are ground to the desired level. A tolerance of about less than ±0.015 inches (0.4 mm) may be achieved to provide consistent flat and level surface for precise height for successive stacking of the units. Since the bottom of the unit may be molded on a flat surface, a consistent and precise block height may be achieved by only grinding the top surface 610 .
[0040] A corner unit 700 according to an exemplary embodiment of the invention is shown in FIGS. 7A, 7B , and 7 C. The corner unit 700 has a front section 702 and a rear section 704 . The corner unit 700 also has a side section 706 coupling the front section 702 and the rear section 704 . One or more webs 708 couple the front section 702 to the rear section 704 . The corner unit 700 may be positioned at the corner of a constructed wall as shown in FIG. 2 . The side section 706 provides a uniform appearance at the end of a row of units and provides support for successive rows of units. The corner units may be stacked alternating by 90 degrees for each row. This provides a lacing of rows between two linear portions of the structure. The cell of the corner units 700 may be filled with concrete to lock the corner units 700 together. The corner units 700 may also be grinded during the manufacturing process to also provide a consistent level surface for precision height control.
[0041] The web 708 is spaced to receive lugs from a previous row of stretcher units off-set by half a unit length. The web is spaced within the corner unit so as to align on top of the web of a previous row of stretcher units allowing the lugs of the previous row of stretcher units to straddle the web. The corner unit may also be used in the construction of a linear position of a wall as shown in FIG. 3 . The corner unit 700 may also have a beveled or chamfered profile on the outer surface of the front section 702 and rear section 704 . The corner unit 700 may also have a chamfered side edge for coupling to adjacent units. In addition, the stretcher unit may have a knock-out portion for producing a bonding-beam. These features are similar to those previously described herein with respect to the exemplary embodiment disclosing the exemplary stretcher unit 400 with angled webs.
[0042] The stretcher units may assemble into a linear wall structure 800 as shown in FIGS. 8A and 8B . The linear cells 802 of the stretcher and/or corner units produce a vertical post. The vertical posts typically may be reinforced with a reinforcement member, for example, steel rebar. The linear cells 802 of the stacked stretcher units provide a more consistent size and are aligned linearly. When concrete is poured into the cells the more consistent size of the linear cell makes it less difficult to install reinforcement members in the cores to form the vertical posts. In addition, the more uniform cell dimensions may make it less difficult to fill the voids within the cell. Many conventional dry stack block systems may provide little or no damming capacity when filling the cells of a dry stack block wall structure.
[0043] FIG. 9 is a perspective view of the stretcher unit stacked according to an exemplary stacking embodiment 900 . The dimensions and structure of the stretcher unit provide the ability to stack a single column of units. By alternating each successive unit by 180 degrees the next stretcher unit may be stacked on top of a successive unit. The lugs of the stretcher units align in the cells of each successive stretcher unit.
[0044] An exemplary embodiment of the invention includes a beveled or chamfered edge profiles. The beveled edge may extend around the both sides and the top edges of the stretcher unit as previously discussed in FIGS. 6A through 6D . The beveled edge of FIGS. 6A through 6D may about a 3/16 of an inch step. The beveled edges of the stretcher unit give the wall a more traditional block construction look. The beveled edge outlines the profile of the block without the need for grouted joints or may be grouted to provide a more detailed masonry profile look.
[0045] Referring to FIGS. 10A and 10B , the exemplary embodiments may include a chamfered or beveled edge 1010 on one side and the top edges and a flat edge 1012 of the stretcher unit 1000 . The chamfered edge 1010 of FIGS. 10A and 10B may about a ⅜ of an inch step. This allows the chamfered edge 1010 to butt directly against a flat edge of the next unit. The chamfered edge 1010 mated against the flat edge of the next unit aids in concealing the joint between the two units from the eye. The chamfered edge 1010 outlines the profile of the block and draws the eye away from the joint between units without the need for grouted joints. The chamfered edge 1010 may also be used to provide a tuck point/mechanical gripping for veneer, stucco or grouted lines to provide a more detailed masonry profile look. Positioning the joint to one side of the chamfered edge 1010 may also conceal any future cracks or separation of the tuck point.
[0046] Referring to FIGS. 10B and 10C , a recess 1014 may be provided between the top surface 1009 and lugs 1004 . The recess may allow the grinding of the top surface 1009 without the lug 604 interfering with the grinding of the top surface 1009 during the manufacturing process. Interference of the lugs may prevent accurate grinding of the top surface 1004 and/or cause destruction or deformation of the lugs 1004 by the grinder. In addition, the recess 1014 may allow for removal of debris from the grinding process or other manufacture process. Debris that remains on the top surface 1009 may prevent successive units from sitting level on each successive layer. The recess 1014 may be molded to extend about ⅛ to ¼ of an inch below the top surface 1009 and provide a gap of about ⅛ to ¼ of an inch. The recess 1014 may also be molded to open away from the center of the lug 1004 so that gravity aids in removal of the debris out of the recess 1014 .
[0047] Modifications may be made to fit particular operating requirements and environments as will be apparent to those skilled in the art, the invention is not considered limited to the examples chosen for purposes of disclosure, and covers all changes and modifications which do not constitute departures from the true spirit and scope of this invention. Modifications and substitutions by one of ordinary skill in the art are considered to be within the scope of the present invention.
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Generally, the invention is a dry stack building block for constructing a masonry wall. The dry stack unit has a front section having an outer surface, an inner surface, a bottom surface, and a top surface. The dry stack unit also has a rear section substantially parallel to the front section having an outer surface, an inner surface, a bottom surface, and a top surface. Two or more webs coupling the inner surface of the front section to the inner surface of the rear section have a top surface and a bottom surface. Two or more pairs of lugs may extend above the top surface of the front section and the top surface of the rear section. Each pair of lugs may have a first lug offset from a second lug in an axis perpendicular to the inner surfaces of the front section and the back section.
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BACKGROUND
[0001] Vehicle manufacturers are equipping many of their vehicle infotainment systems with dashboard mounted display devices. Some of them have pressure-sensitive display, while others do not.
[0002] With the convergence of consumer and automotive environments, vehicle manufacturers are trying to incorporate consumer-related applications into their vehicles. These applications are much like the applications designed for a smart phone that rely on capacitive touch screen and sensors embedded in the phone to interact with the applications.
[0003] A problem with prior art infotainment systems is that the display devices used with them might not be touch sensitive. Displays which are touch sensitive may not have capacitive touch functionality. Moreover, a dashboard-mounted display might be out of reach from the driver's seat, preventing a driver from interacting with the display by touch.
[0004] Some vehicles that have infotainment systems might not have the sensors built in the vehicle required for the applications to work. Vehicles that have already been shipped and not designed for these applications cannot be retrofitted easily or cost-effectively because they would need to add the sensors and/or touch screen input devices.
[0005] An apparatus that can overcome the shortcomings of existing infotainment systems would be an improvement over the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a depiction of a motor vehicle;
[0007] FIG. 2 depicts a dashboard of a motor vehicle;
[0008] FIG. 3 is a block diagram of an apparatus configured to receive control signals from a remote, hand-held communications device; and
[0009] FIG. 4 is a flow chart depicting a method of controlling a vehicle information apparatus.
DETAILED DESCRIPTION
[0010] FIG. 1 is an elevation view of a vehicle 100 . As shown in FIG. 2 , the vehicle 100 has a dashboard 200 comprised of various controls and displays. The controls include a transmission shift lever 202 , air conditioning outlet vents 204 , a headlight control switch 206 , a parking brake release lever 208 amongst others not shown. The displays include a speedometer 210 , a transmission quadrant indicator 212 , a fuel gage 214 and a display screen 220 amongst others.
[0011] The display screen 220 is preferably embodied as a back-lit liquid crystal display having a pressure-sensitive membrane, not visible in FIG. 2 , by which icons or softkeys displayed on the screen under computer control can be actuated using techniques and methods well-known in the art.
[0012] A problem with pressure sensitive or resistive screens used in the prior art is that they are only able to detect one finger of a user at a time. Such screens are generally used for the display of softkeys and icons the actuation of which controls a vehicle function as would otherwise take place by a switch closure.
[0013] Many vehicles are now manufactured with entertainment systems. These systems can include global positioning systems (GPS), video players and display devices, and wireless communications devices. Many of the functions or components in such multi-media systems would be easier to control using a capacitive touch screen, such as those found on portable computer devices that include tablet, personal computers such as the iPad® and in virtually every so called smart phone.
[0014] FIG. 3 is a block diagram of an apparatus 300 for a vehicle 100 , the apparatus 300 providing a control link between a multi-media system in a vehicle and having a display device 220 and a remote located, hand-held input device.
[0015] The apparatus 300 in FIG. 3 is comprised of the aforementioned vehicle-mounted display device 220 . The display device 220 is coupled to a computer 302 by a display bus 304 . The computer 302 executes program instructions stored in a memory device 306 . The memory device 306 is depicted in FIG. 3 as being coupled to the computer 302 via a bus 308 however, the memory 306 and the computer 302 can be co-resident on the same silicon die, as those of ordinary skill in the art will recognize. FIG. 3 depicts a communications interface 310 . The communications interface 310 is couple to the computer 302 via a control bus identified by reference numeral 312 .
[0016] The computer 302 reads program instructions stored in the memory 306 and executes those instructions. The program instructions in the memory 306 cause the computer 302 to perform a variety of functions including displaying various images on the display device 220 but also to communicate with the communications interface 310 . The communications interface 310 is configured to provide to the computer 302 via the bus 312 information-bearing signals that the communications interface 310 receives from one or more portable input devices one of which is shown in FIG. 3 and identified by reference numeral 314 .
[0017] In one embodiment, the portable input device 314 is a smart phone, such as the iPhone® which is comprised of a capacitive touch screen but which is also provided with radio communications equipment by which an information bearing radio frequency signal 316 can be sent to the apparatus 300 from the portable input device 314 . In one embodiment, the portable input device 314 and the communications interface 310 are configured to communicate with each other using these so called Bluetooth communications standard or derivatives thereof. In another embodiment, the portable input device 314 and the communications interface 310 communicate with each other with one or more communications standards published by the Institute for Electrical and Electronics Engineers (I.E.E.E.) 802.11(a),(b),(g),(n) and derivatives thereof.
[0018] Programs executing on the portable input device 314 are already in existence that recognize tactile inputs to a display screen 318 on the portable input device 314 . The inputs to the display screen 318 include but are not limited to gestures using two fingers by which the image displayed on the screen 318 can be enlarged or magnified, scrolled or reduced in size. Other inputs to the display screen 318 and which are supported by existing applications include handwriting recognition. Existing applications executed on the portable input device 314 imbue the display screen 318 with characteristics identical or substantially identical to the capacitive touch pads commonly found on laptop computers. Such pads include the ability to scroll and execute “clicks” by a user placing a fingertip or other object against the display screen 318 sliding it along the screen surface and tapping the screen service respectively.
[0019] Radio frequency communications equipment inside the portable input device 314 and well-known to those of ordinary skill in the art, transmit information-bearing radio frequency signals 316 to an antenna 320 within the apparatus 300 . Signals received at the antenna 320 are recovered by the communications interface 310 . Information in the radio frequency signals 316 is recovered and forwarded to the computer 302 via the bus 312 . The computer 302 then interprets the commands entered at the display screen 318 and actuates the vehicle-mounted display device 220 accordingly.
[0020] FIG. 3 shows that the computer 302 is connected to another bus identified by reference numeral 322 . The bus 322 is a vehicle bus network, known to some in the art as a controller area network. The vehicle bus network 322 , like any other bus which is a set of parallel conductors in a computer system that form a main transmission path, the vehicle bus network 322 couples the computer 302 to one or more vehicle components that are controlled or controllable by the computer.
[0021] The vehicle components that are controlled by the computer as depicted in FIG. 3 include a vehicle climate control system 324 . In other embodiments, the apparatus 300 and the computer 302 are coupled to a broadcast radio receiver 326 which is controlled by the computer 302 . Interior lighting modules 328 , an electronic odometer 330 , a vehicle security system 332 and in some embodiments a driver's seat controller 334 are coupled to the vehicle bus network 322 and therefore controllable through inputs to the vehicle-mounted display 220 .
[0022] FIG. 4 is a flowchart of a method of controlling a vehicle information display apparatus. The method finds particular application to the apparatus depicted in FIG. 3 .
[0023] As a first step, the method includes receiving signals that the communications interface 310 . Such signals can include those from the aforementioned portable input device 314 , however, they can also include signals from other devices. Such other devices can include but are not limited to a global positioning system device, a text-to-speech converter, a voice recognition engine in a smart phone or other wireless device, a camera, an accelerometer, a gyroscope, a light sensor, a compass and a near field communications sensor. These input signals can be from distinct devices, or all coming from a single device.
[0024] Upon receipt of a signal, such as the radio frequency signal 316 at the communications interface 310 , the communications interface 310 extracts a command or user input from the received signal as shown in step 404 . At step 406 an extracted command or user input is forwarded to the computer 406 for execution as if the sensors were designed into the vehicle during production.
[0025] As stated above, the computer 302 executes program instructions stored in the memory device 306 by which it receives commands or inputs from the user interface 310 and processes them or executes them accordingly.
[0026] In step 408 of FIG. 4 , the method depicts the processing of a command or user input. Such processing would include of course the display of map information from a GPS system on the display device 220 . It would also include the display of turn by turn directions.
[0027] In other embodiments, wherein the portable device 314 is another type of interface, program instructions in the memory 306 would cause the computer 302 to display images or video from a camera; text after being converted from handwriting by either the portable device 314 or software in the memory 306 .
[0028] In other embodiments, the input device 314 can include voice recognition capability provided by a smart phone, an accelerometer, a gyroscope, a light sensor, a compass or near field communications sensor. Information from such sensors that is received by the communications interface 310 is processed by the computer 302 and appropriately displayed or activated on the display device 220 .
[0029] In a preferred embodiment, the communications interface 310 is comprised of a radio frequency transceiver configured to transmit and receive signals in the WI-FI spectrum, Bluetooth or other short-range communications system. In an alternate embodiment, the communications interface 310 provides a universal serial bus or USB interface. Still other embodiments include the communications interface that provides Ethernet, media-oriented systems transport or most communications, RS232, Fire Wire and HDMI or High-Definition Multi-media Interface.
[0030] In yet another embodiment, the communications interface 310 receives an audio signal as either a digital signal such as a MP 3 file, an analogue signal or a digital representation thereof. The analogue signal once provided to the computer 302 is processed by the computer 302 into an audible signal and output from a speaker 338 .
[0031] Referring again to FIG. 3 , one or more cradles that are connected to interior panels which couple an input device electrically to the computer 302 and mechanically to the vehicle 100 . Cradles for cellular telephones are well-known in the art. Further description of them is omitted for brevity.
[0032] In yet another embodiment, a second cradle substantially identical to the first is provided by which two smart phones or two other input devices can provide inputs to the computer 302 via the communications interface 310 . In such an embodiment the two input devices in the two cradles can both effectuate control of a program running on the computer from programs stored in memory device 306 . An example of such a program would be a game, a navigations system or an audio playback device by which two or more passengers could interact with each other via the communications interface 310 .
[0033] The foregoing description is for purposes of illustration only. The true scope of the invention is set forth in the appurtenant claims.
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A vehicle display device is provided with a communications interface, which couples the vehicle display device to portable input devices inside the vehicle. The portable input devices are thus provided with the ability to control the display device and what is displayed thereon. The communications interface also enables the portable input device to control vehicle subsystems such as a climate control system, entertainment system and the like. Portable input devices equipped with sensors have sensor-generated information displayed on the vehicle display device.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation under 35 U.S.C. 120 of commonly assigned prior U.S. application Ser. No. 10/726,047, filed Dec. 2, 2003 in the name of Aakash Bordia, now allowed.
FIELD OF THE INVENTION
[0002] The present invention relates generally to electronic communication systems, and more specifically to a method and system for excluding recipients in an electronic communication system using an exclude operation.
BACKGROUND OF THE INVENTION
[0003] Today's electronic communication systems are heavily relied on to support a wide variety of user needs. In particular, electronic mail software programs (“email”) have become ubiquitous, and are often the most practical and/or efficient mode of communication available. However, user accessible controls over entities designated for receipt of an outgoing message are limited in typical systems. The entities processed in such systems may be mailing and distribution lists, user-defined groups, individual email addresses, aliases, or other specific types of recipient identifiers as appropriate for the specific communication system. Accordingly, in the present application, lists, groups, aliases and recipients are interchangeably referred to as entities.
[0004] For example, a user of existing email client-server software, such as Lotus Notes®, Microsoft Outlook Express®, Eudora®, or sendmail™, does not have the ability to easily exclude an entity from an ongoing or initial communication, when using mailing lists, groups, and/or individual addresses. For example, an email program user may desire to send an email message to recipients listed in association with an email alias or a mailing list for a set of users, such as “Sales Employees”, while excluding one or more entities within the list from receiving the message. Existing systems provide no convenient mechanism for accomplishing this objective. As a result, the user may be forced to individually input all the entities from the list other than the one(s) they wish to exclude into the destination field for the message. Similarly, if it is desired to exclude an entity from receiving an initial message or ongoing email thread, the current approach is to manually search and delete the unwanted recipient address or lists from destination fields. This shortcoming prevents the convenient use of the “Reply All” function in situations where one or more entities participating in a communication thread are intended to be excluded from a message within the ongoing series of communications.
[0005] This problem becomes more difficult in the case of a message in which the only receiving entities specified are specified as lists or groups. First, there is no convenient way to determine the individual email recipients of the message, without some automated way to resolve the component entities of each destination list on the client system. Existing systems do not operate to determine the individual addresses specified by each destination list or group, unless the list or group is local to the client. Moreover, even if the all destination lists and/or groups are fully resolved, the user of the client system must then manually search and delete those entities desired to be excluded from receiving the message.
[0006] In the area of bulk email software, sometimes referred to as “spamming” tools, some recipient exclusion capabilities exist. Existing bulk email tools provide the ability to define a recipient exclusion file separate from and outside the user interface for defining, addressing and sending a specific message. Accordingly, such list definition tools are not suitable for general email users, since the exclusion step, even for a single message, requires list manipulation independent from the steps of defining and/or responding to a message. Switching to another window within the user interface window to perform such list editing and/or definition is undesirable from a usability perspective. Moreover, separate list editing steps may be cumbersome when defining and/or responding to individual messages, such as within a message thread using a “Reply All” function. Editing an exclusion file for a small number of desired exclusions is, like manually searching and editing the contents of message destination fields to delete individual recipients, time consuming and inefficient. Thus, while existing bulk email tools are useful for batch processing of “spam” email messages, their overall design and user interfaces leave much to be desired for the general email user.
[0007] For the above reasons, it would be desirable to have a new system for controlling the recipients of an electronic message, such as an email message. The system should allow a user to exclude recipients as easily as it allows the user include recipients of a message.
SUMMARY OF THE INVENTION
[0008] To address the problems described above and others, a method and system are disclosed that enable a communications system user to conveniently define entities to be excluded from receiving an electronic communication, such as an electronic mail (“email”) message. In an illustrative embodiment, the disclosed system provides an “Exclude” user entry field in a user interface to an email system. The Exclude field accepts entry of an “exclude set” of entities to be excluded from being recipients of an email message being processed or defined in a currently accessible graphical user interface window. The disclosed Exclude field is provided in a user interface window together with one or more other user entry fields available for definition and/or review of an “include set” of entities initially designated for receipt of the message.
[0009] The user entry fields available for definition and/or review of an “include set” may, for example, include a cc: (“carbon copy”) user entry field, a bcc: (“blind carbon copy”) user entry field, as well as the To: user entry field. The bcc: user entry field lists addresses, groups, or lists, to which the message will be sent, but which will not be seen by the recipients, while the contents of the cc: field will be visible to all recipients.
[0010] The disclosed system is applicable to a variety of communication systems, such as email and other similar methods of communication. The entities processed using the disclosed system may be mailing and distribution lists, user-defined groups, individual email addresses, aliases, or other specific types of recipient identifiers as appropriate to a specific communication system. In some cases, multiple recipients are addressed by a single recipient identifier, like an email address. The specific title or image identifying the Exclude field may include a text title of “Exclude”, or provide any other textual or graphic indication of the field, as appropriate. The Exclude field may be adjacent to the fields defining the include set, or in some other location within the user interface window. The disclosed system processes one or more entities identifiers entered by a user into the Exclude field by preventing those entities from receiving the email/communication. Accordingly, the disclosed system may be used to exclude an individual within a group or list from receiving a message, or to exclude irrelevant users from receiving a message otherwise received by all recipients in an ongoing email thread in which recipients are replying to all users within a group using a “Reply All” email function. The disclosed system can be used to exclude any specified set of entities from the set of recipients.
[0011] The disclosed system provides significant advantages over the prior art. Specifically, the disclosed system enables a user to exclude recipients from an ongoing discussion using email, as easily as the user can add recipients to the ongoing discussion. The disclosed system may further operate to process email groups and/or lists by resolving their contents on either the client or server side. Moreover, in contrast to bulk email systems designed to send large numbers of copies of a single email message, the present invention automates the exclusion of entities from individual messages in a way that is useful to the general email user. For many users, this will translate into a) saving keystrokes, and b) eliminating the trouble of remembering all the entities on a list or in a group. The disclosed system also potentially reduces network traffic and disk space usage, since the amount of overall traffic is reduced through its use.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In order to facilitate a fuller understanding of the present invention, reference is now made to the appended drawings. These drawings should not be construed as limiting the present invention, but are intended to be exemplary only.
[0013] FIG. 1 is a block diagram illustrating devices in an embodiment of the disclosed system.
[0014] FIG. 2 is a block diagram representation of a screen display showing a client email user interface for an embodiment of the disclosed system;
[0015] FIG. 3 is a flow chart illustrating operation of a source client computer system an embodiment of the disclosed system; and
[0016] FIG. 4 is a flow chart illustrating operation of a source server in an embodiment of the disclosed system.
[0017] FIG. 5 is a flow chart illustrating operation of a destination server in an embodiment of the disclosed system.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0018] As shown in FIG. 1 , devices in an illustrative embodiment of the disclosed system include a source client system 1 communicably coupled to a source server system 2 . The source server system 2 is communicably coupled to a network 3 , over which it communicates with a number of destination server systems, shown for purposes of illustration as destination server system 4 . The destination server system 4 is communicably coupled with some number of destination client systems, shown as destination client systems 5 , 6 and 7 .
[0019] The source client system 1 , source server system 2 , destination server system 4 , and destination client systems 5 , 6 and 7 are, for example, each computer systems having one or more processors, as well as associated memory for storing program code executable on such processors. Such computer system may be based on any appropriate any specific computer architecture and/or operating system, and the program code may be provided to the processor and/or stored in the associated memory using any appropriate programming language and/or data format. For purposes of explanation, the source client 1 and destination clients 5 , 6 and 7 each execute electronic mail (“email”) client programs. The source server 2 executes an email server program associated with the email client program in the source client 1 , while the destination server 4 executes an email server program associated with the email client programs in the destination clients 5 , 6 and 7 .
[0020] As shown in FIG. 2 , an embodiment of the disclosed system operates to provide a graphical user interface (GUI) display including a message processing display object or window, such as the electronic mail (“email”) client program user display 10 . The email client user display 10 is displayed, for example, to a user of client software in an email client-server software system, such as a user of the source client system 1 of FIG. 1 . In the embodiment of FIG. 2 , the client user display 10 is provided within a single window of a window based user interface, such as that may be provided by a window manager program in a windowing system within an operating system executing on the client computer system. The window containing the client user display 10 may, for example, be provided as a separate viewing area on a computer display screen in a system that allows multiple viewing areas as part of the graphical user interface (GUI).
[0021] As shown in the illustrative embodiment of FIG. 2 , the client user display 10 is generated including a destination user entry field, shown as the To: user entry field 12 , a carbon copy user entry field, shown as the cc: user entry field 14 , a blind carbon copy field, shown as the bcc: user entry field 16 , an exclude user entry field, shown as the Exclude: user entry field 18 , a subject line user entry field, shown as the Subject: user entry field 20 , and a message definition portion, shown as the message 22 in FIG. 2 .
[0022] FIG. 3 is a flow chart showing steps performed at a source client system, such as the source client system 1 of FIG. 1 . As shown in FIG. 3 , at step 30 the source client accepts the include set and exclude set as inputs from the user, for example through an interface such as shown in FIG. 2 . For example, the include set consists of the entities present in the destination, carbon copy, and blind carbon copy user entry fields 12 , 14 , and 16 of FIG. 2 . The contents of the destination, carbon copy, and blind copy fields may be explicitly entered by the user in the current display window, or may be preloaded as a result of the user using a Reply or Reply all function or other client configuration with regard to a previously received message through the email client program interface. The exclude set consists of the entities present in the exclude user entry field, such as the Exclude: user entry field 18 of FIG. 2 . The contents of the exclude field may also be explicitly entered by the user in the current display window, or may be preloaded as a result of the user using a Reply or Reply all function with regard to a previously received message through the email client program interface. The entities within the include set and the exclude set may consist of individual user addresses, address lists, user-defined groups, user-defined aliases, or other indications of potential recipients of the current message.
[0023] At step 32 , the source client system resolves any unresolved entities in the include set or exclude set that it can resolve, either locally based on information stored in the source client system, or by contacting a remote entities processing facility. For example, a remote entities processing facility employed at step 32 could consist of an email server software executing on the source server 2 of FIG. 1 , or a directory server, or some other facility. In the exemplary embodiment, resolution of entities in the include set or exclude set means, for example, that identifiers in the sets are translated into one or more email addresses, each of which having a destination server IP (Internet Protocol) address associated with them. Step 32 may include determining which entities within the include and exclude sets indicate multiple recipients, as in the case of a distribution list or user defined group. For such entities, the source client system attempts to determine the individual recipient identifiers, such as email addresses, associated with them. After the entity resolution performed at step 32 , there are, for example, entities in both the include set and the exclude set, which may be either resolved or unresolved.
[0024] At step 34 , the include set is now assigned the difference between the include set and the exclude set. The exclude set remains the original exclude set. Accordingly, at step 34 , the following set theory difference operation is performed:
[0000] INCLUDE SET={INCLUDE SET−EXCLUDE SET}
[0025] As a result, the include set contains all members of the include set that do not belong to the exclude set. As will be apparent to those skilled in the art, the include set cannot be empty initially, while the exclude set can be empty.
[0026] At step 36 , the disclosed system determines whether the include set resulting from step 34 is empty. If so, then the flow ends at step 38 . Otherwise, the new include set, exclude set, and message are sent to a source server, such as the source server system 2 of FIG. 1 , for further processing.
[0027] FIG. 4 is a flow chart showing steps performed by a source server system, such as the source server system 2 of FIG. 1 , in an embodiment of the disclosed system. As shown in FIG. 4 , email server software executing on the source server system accepts the message transmitted from the source client system, as described at step 40 of FIG. 3 , together with the include and exclude sets. At step 52 , the source server system operates to resolve the include set and the exclude set, by resolving any unresolved entities in the include set or exclude set that it can resolve. At step 54 , the source server system may operate to determine whether a resolution error has occurred. A resolution error occurs when the source server is unable to resolve all the entities in the include and exclude sets it received to their respective destination IP addresses. If such an error occurs, then step 54 is followed by step 56 , in which an error may be sent back to the source client system stating that one or more entities could not be resolved, and processing of the message may be terminated. Otherwise, step 54 is followed by step 58 , at which the source server system assigns the difference between the include set and the exclude set to the include set. The exclude set remains unchanged. If the resulting include set is determined to be empty at step 60 , then processing is completed at step 62 . Otherwise, step 60 is followed by step 64 , in which the disclosed system operates to send the message to the entities in the new include set, and also passes along the exclude set with each message. Those skilled in the art will recognize that the forwarded message implicitly includes the relevant include set for any given destination server, for example, a message sent to user1@ibm.com, user2@ibm.com and user3@xyz.com will implicitly include {user1,user2} as the include set for destination server ibm.com, and {user3} as the include set for destination server xyz.com.
[0028] FIG. 5 is a flow chart showing steps performed by an embodiment of the disclosed system to process information received by a destination server system, such as the destination server 4 of FIG. 1 . The destination server may or may not support exclusion of recipients, and the disclosed system can operate whether or not such exclusion is supported on the destination server. At step 70 , the destination server accepts the incoming message from the source server, which may include the exclude set. At step 72 , the destination server may operate to resolve one or more entities within the exclude set and include list that it received with the message from the source server. At step 74 , in the event that a difference operation on the include set and exclude set has a non-null result, the destination server deposits the received message to the set of entities indicated by the difference between the include set and the exclude set, for example by transmitting the message to one or more destination clients such as the destination client systems 5 , 6 and 7 shown in FIG. 1 . The destination server may operate as a source server system for messages sent to other destination server systems, for example for messages originating the destination client systems communicably coupled with the destination server system. Also, the destination server may operate as a source server for messages received from other source server systems, for example for entities in an incoming message's include set resolves into one or more recipients which are not within the domain of the destination server. In such a case the source server functions as a virtual source client of the destination server.
[0029] In an example of operation of the disclosed system, a distribution list may be defined as the ALL-Employees list, and contain 2000 individual user entities, each consisting of an individual email address. A user may desire to send an email message to those users within the All-Employees list, but to exclude a particular user, identified an individual email address John-Smith company. The user needs to simply enter the All-Employees list identifier into the To: user entry field 12 of FIG. 2 , and also enter the email address John-Smith company into the Exclude: user entry field 18 , and then click on a “send” button provided by the email client software. Similarly, if the user desires to send a message to the All-Employees list, but to exclude 80 users listed in a list identified as the Federated-Team list, the user needs simply to enter the All-Employees list identifier into the To: user entry field 12 of FIG. 2 , and also enter the Federated-Team list identifier into the Exclude: user entry field 18 , prior to clicking on a “send” button provided by the email client software. Moreover, if, during a message thread being communicated among all users listed within the All-Employee list, the user receives a message, and wishes to send a reply excluding the users within the Federated-Team list. The user need only use a Reply or Reply all function, and then enter the Federated-Team list identifier into the Exclude: user entry field 18 , prior to clicking on the “Send” button provided by the email client software.
[0030] FIGS. 3 , 4 and 5 are flowchart illustrations of methods, apparatus (systems) and computer program products according to an embodiment of the invention. It will be understood that each block of the flowchart illustrations, and combinations of blocks in the flowchart illustrations, can be implemented by computer program instructions. These computer program instructions may be loaded onto a computer or other programmable data processing apparatus to produce a machine, such that the instructions which execute on the computer or other programmable data processing apparatus create means for implementing the functions specified in the flowchart block or blocks. These computer program instructions may also be stored in a computer-readable memory that can direct a computer or other programmable data processing apparatus to function in a particular manner, such that the instructions stored in the computer-readable memory produce an article of manufacture including instruction means which implement the function specified in the flowchart block or blocks. The computer program instructions may also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart block or blocks.
[0031] Those skilled in the art should readily appreciate that programs defining the functions of the present invention can be delivered to a computer in many forms; including, but not limited to: (a) information permanently stored on non-writable storage media (e.g. read only memory devices within a computer such as ROM or CD-ROM disks readable by a computer I/O attachment); or (b) information alterably stored on writable storage media (e.g. floppy disks and hard drives).
[0032] While the invention is described through the above exemplary embodiments, it will be understood by those of ordinary skill in the art that modification to and variation of the illustrated embodiments may be made without departing from the inventive concepts herein disclosed. Moreover, while the preferred embodiments are described in connection with various illustrative program command structures, one skilled in the art will recognize that the system may be embodied using a variety of specific command structures. Accordingly, the invention should not be viewed as limited except by the scope and spirit of the appended claims.
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A system that enables a communications system user to conveniently define entities to be excluded from receiving an electronic communication, such as an electronic mail (“email”) message. An “Exclude” user entry field is provided in a user interface to a communication system. The Exclude field accepts entry of an “exclude set” of entities to be excluded from an email message being processed or defined in a currently accessible graphical user interface window. The disclosed Exclude field is provided in a user interface window together with one or more other user entry fields available for definition and/or review of an “include set” of entities initially designated for receipt of the message. Lists and/or groups may be resolved by determining the destinations they contain either within the client computer system, within a source server computer system, and/or within a destination server computer system.
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BACKGROUND OF THE INVENTION
The invention relates to an electric sewing machine, and more particularly relates to a speed control system for such a sewing machine, in which a single operating part is operated in one direction to start and stop the sewing machine. The operating part is pushed in one direction in one way to make effective an ordinary speed selecting circuit, and is pushed in the same direction in another way to make effective an extreme lower speed control circuit. The single operating part is also touched by the operator during a stitching operation to change over from the ordinary speed selecting circuit to the extreme speed control circuit.
Many devices have been provided for such a speed control of sewing machine. Such conventional speed control devices, however, have been complex in structure and rather difficult in operation.
The present invention has been provided to eliminate the defects and disadvantages of the prior art.
It is a primary object of the invention to provide a sewing machine with a speed control system which is simple in structure and easy in operation.
It is another object of the invention to heighten the operational safety of a sewing machine.
SUMMARY OF THE INVENTION
In keeping with these objects the invention consists of a sewing machine equipped with a machine drive motor, an upper shaft having a detector for counting the number of revolutions the shaft executes, and a motor speed control system including a variable motor speed control circuit. The variable motor speed control circuit establishes the speed at which the motor will operate when the control circuit is operative to permit the variable speed control to determine the motor speed.
The motor control system is composed of an electrically conductive operating means which senses the touch of the operator; a switch means operated by manipulation of the electrically conductive means and which produces a signal; a bistable functioning means to start the machine drive motor when it is stopped in response to the signal from the switch means. This bistable functioning means may be a T-type flip-flop circuit. The motor control system also responds to stop the motor when the bistable functioning means receives a signal from the switch means while the motor is rotating.
Another feature of the invention is an extreme lower speed control which may take the form of an AND circuit. This circuit is operative to drive the machine motor at an extreme lower speed when the conductive operating means is touched by the operator while the motor is running.
An additional aspect of the invention is formed by arranging a time delay means between bistable functioning means and the extreme lower speed control. This circuit maintains the motor speed at the same level the speed had before the electrically conductive operating means was touched unless the operator maintains contact with the conductive operating means for a specified time interval in which case the extreme slow speed will result.
Yet another feature of the invention resides in the use of two counter means. The first means is set by the repeated touching of the electrically conductive operating means. The number of touches sets the counter for the purpose of executing said number of stitches. The second counter is connected to the detector on the upper shaft and thus counts the number of stitches that are executed after the counter system is engaged. This aspect of the invention also utilizes a comparator means to compare the two counters and to stop the motor when the two counters have the same values. Other aspects of the invention provide for no signals from the comparator means when the first counter is set at zero and for the resetting of the counters at zero upon completion of the operation.
The other features and advantages of the invention will be apparent from the following description of preferred embodiments of the invention in reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a sewing machine provided with the invention,
FIG. 2 is a control block circuit of the invention,
FIG. 3 is another embodiment of the control block circuit,
FIG. 4 is another perspective view of a sewing machine provided with a different embodiment of the invention, and
FIG. 5 is another embodiment of the control block circuit as shown in FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In reference to FIGS. 1 and 2, a sewing machine 1 is provided with an operating element 2 as shown, which is electrically conductive, but is electrically isolated from the sewing machine 1. The operating element 2 is connected to a contact switch circuit SA, which senses the touch of the operating element 2 by the operator's finger and operates to make effective an extreme lower speed control circuit. The operating element 2 is also pushed by the operator to operate a switch 4, which makes effective a normal speed control circuit, and makes effective a control to stop the sewing machine if it is running. The sewing machine 1 is also provided with speed changeover switches 3 each operated to change the machine speed to low, medium and high speeds respectively. The output of the switch 4 is connected to an input circuit SC which has an electric wave rectifying function and a chattering prevention function. The output of the input circuit SC is connected to the trigger terminal T of a T-type flip-flop circuit FF 1 . The flip-flop circuit FF 1 is employed to start and stop the sewing machine, and is reset by the rising signal when the control power source is applied. The flip-flop circuit FF 1 has a true side output Q connected to a first input of an AND circuit AND 1 and also connected to a second input of the AND circuit AND 1 via a delay circuit TD.
The AND circuit AND 1 is a principal part of the extreme lower speed control circuit, and has a third input connected to the output of the contact switch circuit SA. The AND circuit AND 1 has an output connected to a set terminal S of a flip-flop circuit FF 2 . The flip-flop circuit FF 2 has a set terminal R connected to the complement side output Q of the flip-flop FF 1 , and has a true side output Q connected to an extreme lower speed setting input S of a speed setting circuit SS. The speed setting circuit SS, when the input S is high level, operates the machine motor M constantly at an extreme lower speed via a drive circuit DV. The true side output Q of the flip-flop FF 1 is connected to a first input of an AND circuit AND 2 . The AND circuit AND 2 has another input connected to the complement side output Q of the flip-flop circuit FF 2 , and has an output connected to a variable speed setting input V of the speed setting circuit SS, which, when the input V is igh level, is operated by a signal from the manually operated changeover switches 3 to drive the machine motor M via the drive circuit DV at a low, medium or high speed. When the inputs S and V are low level, the speed setting circuit SS is operated to stop the machine motor M.
With such a structure of system, if the control power source is applied, the flip-flop FF 1 is reset, and accordingly the flip-flop FF 2 , which receives the complement side output Q of the flip-flop FF 1 , is reset, and accordingly the inputs S and V of the speed setting circuit SS are low level. Therefore, the machine motor M remains standstill. Then if the operator touches the operating element 2, the contact switch SA is operated to make one input of the AND circuit AND 1 high level. However, since the flip-flop FF 1 is reset, the AND circuits AND 1 and AND 2 are low level, and accordingly the inputs S and V of the speed setting circuit SS are low level. Therefore the machine motor M is still standstill. If the operating element is pushed, the switch 4 is closed and the input circuit SC is operated to set the flip-flop FF 1 . If the operator takes the hand off from the operating element 2 before the delay circuit TD is operated, the AND circuit AND 1 remains to be low level and the flip-flop circuit FF.sub. 2 remains to be low level. Therefore, the AND circuit AND 2 becomes high level to operate the machine motor M at a speed determined by one of the speed changeover switches 3. On the other hand, if the operating element 2 is kept as it is pushed for a predetermined time until the delay circuit TD becomes high level, the flip-flop FF 2 is set, and the AND circuit AND 2 becomes low level. As a result, the machine motor M is driven at an extreme lower speed. This is the same as in the case the speed changeover switches are not operated. Then if the operator takes the hand off from the operating element 2, the flip-flop circuit FF 2 is not reset because the flip-flop circuit FF 1 has been set, and the extreme lower speed rotation of the machine motor M is maintained. If the operator touches the operating element 2 while the sewing machine is running at a speed determined by one of the speed changeover switches 3, the flip-flop circuit FF 2 is switched into a reset condition and the machine motor M is rotated at the extreme lower speed. If the operating element 2 is pushed while the sewing machine is running, the switch 4 is closed to reset the flip-flop circuits FF 1 and FF 2 , and the machine motor M is stopped.
FIG. 3 shows a second embodiment of control block circuit, in which the flip-flop circuit FF 2 of FIG. 2 is not used. Instead, the output of the AND circuit AND 1 is connected to the extreme lower speed setting input terminal S of the speed setting circuit SS, and is also connected, through an inverter IN, to the input of the AND circuit AND 2 . In this embodiment, so long as the operator touches the operating element 2 while the flip-flop circuit FF 1 is in a set condition, namely while the sewing machine is running, the AND circuit AND 1 becomes high level to drive the machine motor M at the extreme lower speed. If the operator takes the hand off from the operating element 2, the AND circuit AND 2 becomes high level to return the machine motor M to a set speed determined by one of the changover switches 3.
FIGS. 4 and 5 shows a third embodiment of the invention. Explanation will be made regarding only the modified parts of the first embodiment of the invention as shown in FIGS. 1 and 2.
In reference to FIG. 4, the operating element 2 is further provided with two operating parts 5 and 6 spaced froms each other. The operating element 2 may not be electrically conductive. The operating parts 5 and 6 are electrically conductive and are electrically isolated from the sewing machine 1 and from each other. The operating part 5 is to designate an extreme lower speed rotation of the sewing machine, and the operating part 6 is to designate a desired number of rotations of the sewing machine. As shown in FIG. 6, the two operating parts 5 and 6 are each connected to the contact switch circuit SA. This embodiment is different from the first embodiment of FIGS. 1 and 2 in the point that the embodiment is provided with an additional function to produce a desired number of stitches by operating the operating part 6 so many times.
According to this embodiment, if the operator touches the operating part 6, the contact switch circuit SA receives a touch input 6A. The contact switch citcuit SA has an output connected to the input side of an AND circuit AND 3 and to the input of a counter COUNT 1 . A counter COUNT 2 receives a signal from an upper shaft position detector PD per rotation of the upper drive shaft of the sewing machine to count up the rotations of the upper shaft. The counters COUNT 1 and COUNT 2 have the respective reset input terminals R each connected to the complement side output Q of the flip-flop FF 1 , and are each reset to 0 by a rising signal from the flip-flop when the complement side output Q becomes high level. These counters COUNT 1 and COUNT 2 have the outputs each connected to the input side of a comparator circuit CC, which is operated when the counted values of the both counters come to the same, thereby to make the reset input R of the flip-flop FF 1 high level to reset the flip-flop circuit. A zero-value detector ZD maintains the comparator circuit CC inoperative when the counting value of the counter COUNT 1 is zero, irrespectively of the counting value of the counter COUNT 2 . The AND circuit AND 3 has another input terminal connected to the true side output Q of the flip-flop circuit FF 1 , and has an output connected to one input terminal of an OR circuit OR. The OR circuit has another input terminal connected to the output of the AND circuit AND 1 , and has an output connected to the set terminal S of the flip-flop circuit FF 2 .
With such a structure of the embodiment in FIGS. 4 and 5, if the control power source is applied, the flip-flop circuit FF 1 is reset, and accordingly the flip-flop circuit FF 2 , which receives the complement side output Q of the flip-flop circuit FF 1 , is reset, and accordingly the inputs S and V of the speed setting circuit SS are low level. Then if the operator touches the operating part 3, the contact switch SA is operated to make one input of the AND circuit AND 1 high level. However, since the flip-flop FF 1 is reset, the AND circuits AND 1 and AND 2 are low level, and accordingly the inputs S and V of the speed setting circuit SS are low level. Therefore the machine motor M is still standstill. If the operating element 2 is pushed, the switch 4 is closed and the input circuit SC is operated to set the flip-flop FF 1 . If the operator takes the hand off from the operating element 2 before the delay circuit TD is operated, the AND circuit AND 1 remains to be low level and the flip-flop circuit FF 2 remains to be low level. Therefore, the AND circuit AND 2 becomes high level to operate the machine motor M at a speed determined by one of the speed changeover switches 3. On the other hand, if the operating element 2 is kept as it is pushed for a predetermined time until the delay circuit TD becomes high level, the flip-flop FF 2 is set, and the AND circuit AND 1 becomes low level. As a result, the machine motor M is driven at an extreme lower speed. This is the same as in the case the speed changeover switches are not operated. Then if the operator takes the hand off from the operating element 2, the flip-flop circuit FF 2 is not reset because the flip-flop circuit FF 1 has been set, and the extreme lower speed rotation of the machine motor M is maintained. If the operator touches the operating part 5 while the sewing machine is running at a speed determined by one of the speed changeover switches 3, the flip-flop circuit FF 2 is switched into a reset condition and the machine motor M is rotated at the extreme lower speed. If the operating element 2 is pushed while the sewing machine is running, the switch 4 is closed to reset the flip-flop circuits FF 1 and FF 2 , and the machine motor M is stopped.
Further in a sewing operation, it may often happen that same more stitches are carefully sewn at the end part of a stitching cycle after the sewing machine is once stopped in dependence upon the stitching type or kind. In such a case, if the stitch number designating part 6 is touched by the operator so many times as the operator requires the stitches, the number of touches is counted up by the counter COUNT 1 . In this instance, one input terminal of the AND circuit AND 3 receives and input, but it gives no output because the flip-flop circuit FF 1 is reset, and the machine motor M remains standstill. If the operating part 6, and accordingly the operating element 2 is pushed at the last time of touching, the switch 4 is closed to set the flip-flop FF 1 . At the same time, the output of the AND circuit AND 3 becomes high level and the flip-flop circuit FF 2 is set through the OR circuit OR, and then the machine motor M is driven at an extreme lower speed. The rotations of the machine motor are each counted up by the counter COUNT 2 . If the counting value of the counter COUNT 2 comes to that of the counter COUNT 1 , the comparator circuit CC gives an output to reset the flip-flop circuit FF 1 , and the machine motor M is stopped. At the same time, the counters COUNT 1 and COUNT 2 are reset by the rising signal of the complement side output Q of the flip-flop circuit FF 1 .
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A sewing machine composed of a drive motor, an upper shaft with detector, a motor speed control and a motor starting and stopping control. The motor speed control has a bistable device to start and stop the machine in response to signals from a switch and an extreme lower speed control to drive the motor at an extreme low speed in response to a signal from a switch. Motor speed control also has counters which when set and actuated by a switch execute a predetermined finite number of stitches. Motor control device also has circuits allowing the motor to operate in response to a variable speed control switch.
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BACKGROUND OF THE INVENTION
The present invention pertains to a sewing machine and more particularly to a method and apparatus operatively associated with the machine for attaching an elastic band to a tubular workpiece. Methods of applying an elastic band to a tubular workpiece are well known and usually involve the attachment of the band so that it is exposed or within a folded edge of the workpiece which is accomplished by utilization of appropriate folding guides.
More precisely, the folding of an edge of a workpiece is accomplished by a type of guide that requires constant attention on the part of the operator during the sewing cycle and in particular at the end of said cycle when the initial portion of the seam approaches the opening of the guide.
With the workpiece being of the tubular type, the seam is formed on a ring-like section which causes the initial portion of the seam to approach the guide during the latter part of the seaming cycle. To complete the seaming cycle, the operator must intervene so as to prevent the initial portion of the seam from entering the channel of the guide. This final operation is conducted with the garment completely free, and the success of the operation depends solely on the skill of the operator. This procedure requires what is considered an excessive loss of time due to the necessity of sewing intermittently so as to enable the operator to manually manipulate the edge of the workpiece. Careful attention is also required so as to orient the workpiece in the guide in order to obtain a uniform turning of the folded edge. An object of the present invention is to improve the sewing operation and to eliminate all previously required intervention on the part of the operator during the sewing operation. The technical problem to be solved is that of positioning the workpiece and the elastic band prior to the start of the sewing operation and to provide means for folding the edge of the workpiece onto the elastic band which will not require the use of manual-locking edge guides and which will permit the workpiece to be presented to the sewing area of the machine in readiness for sewing and without the need for further attention during the sewing cycle.
SUMMARY OF THE INVENTION
The solution to this problem involves a method in accordance with the present invention, which includes the following steps:
(a) placement of the workpiece onto a suitable tension device so as to locate the edge of the workpiece in contact with a positioning device;
(b) locating an elastic band on the tubular workpiece at a predetermined distance from the edge thereof;
(c) complete and synchronized folding onto the elastic band of that area of the workpiece intermediate said band and the edge of said workpiece; and
(d) sewing of a complete seam on the folded portion of the workpiece.
To accomplish these method steps requires an apparatus that includes a tensioning device which includes two or more freely rotatably or driven rollers, a positioning element for engaging the edge of the tubular workpiece, which is operatively associated with each of said rollers. Additionally positioning elements are provided for the elastic band, which are operatively associated with each of said rollers and folding elements that engage a portion of the edge of the workpiece and which form an integral part of each of the positioning elements for the tubular workpiece. The folding elements are slightly spaced from each of their associated rollers and cooperate with each of the elastic band positioning elements to effect the folding of the workpiece edge onto the elastic band. The axes of rotation of at least two of the rollers are on the same plane as that of the work surface of the sewing machine.
These and other objects of the invention will become more fully apparent by reference to the appended claims and as the following detailed description proceeds in reference to the figures of drawing wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the device according to the invention operatively associated with a sewing machine;
FIGS. 2, 3 and 4 are elevational views and partially in section taken along line II--II of FIG. 1, showing progressively the steps of effecting the folding of the workpiece edge on the elastic bands; and
FIG. 5 is a sectional view of a portion of the workpiece showing the elastic band within the fold and in readiness for the seaming operation.
DESCRIPTION OF THE PREFERRED EMBODIMENT
For a better understanding of the method provided by the present invention, the apparatus for effecting the abovementioned method steps will first be described.
This apparatus includes a frame that is identified generally in FIG. 1 by numeral 1 and is slidably supported in operative association with a conventional sewing machine 2. The frame includes two vertically extending supports 3, disposed in spaced relation one from the other and which depend from a horizontal cross-bar 4.
The cross-bar 4 is supported by a pair of spaced and parallel guide rods 5 disposed above the sewing machine and are slidably mounted in any suitable structure not shown. The frame 1 includes a tensioning device 6 having a pair of rollers 7 that are rotatably mounted on the lower ends 8 of the vertical supports 3.
Either freely rotatably or driven rollers may be used without altering their intended function.
The axes of rotation of the two rollers 7 are parallel and they are disposed in a plane that is parallel to the work surface 9 of the sewing machine.
This arrangement is such that the two rollers 7 are separated one from the other by a distance greater than the width of the base 10 of the sewing machine, and are for all intents and purposes located at the same height as the work surface 9.
In order to stretch and hold the tubular-type workpiece to be sewn, the tensioning device also includes two auxiliary rollers 11 which are rotatably mounted on the upper portions of the supports 3 that are identified in FIG. 1 by numeral 12.
The rollers 7 and 11 are disposed so as to form a quadrilateral that defines the pathway of the tubular garment as it is being sewn.
Each roller 7 and 11 is provided with a raised ring 13 that is fixed thereon at a predetermined distance from said rollers' inner ends 14 and serve to maintain tension on the workpiece so as to prevent displacement thereof during its subsequent rotation during sewing.
Positioning elements 15 for the tubular workpiece are also provided for each roller on the frame 1 and are mounted adjacent the end parts 8 and 12 of the supports 3.
More specifically these positioning elements 15 are slightly spaced from their respective rollers and define semicircular blocks which in their rest position are spaced from the inner ends 14 of their rollers by a distance equal to that portion of the workpiece which has to be folded with the elastic band interposed therebetween and which will be more fully described hereinafter.
Intermediate each positioning element 15 and its respective roller a folding element 16 is provided which defines an arcuated plate that extends parallel with and at location disposed radially from the outer surface of each roller. These arcuated plates form an integral part of each positioning element 15 and extend in a direction whereby their outer ends are disposed in close alignment with the inner ends 14 of the rollers.
The circumference of the arcuated plates is such that they subtend the inner end of each roller by an amount that is equivalent to the thickness of the workpiece that has been folded and which includes the elastic band.
Consequently, in the case of the preferred embodiment shown in the drawings, the maximum circumference of each arcuated plate is equal to a 90° angle.
Should a tensioning device having only two or three rollers be utilized, the maximum circumference would be equal to a 180° and a 120° angle respectively.
Each of the positioning elements 15 is fixed on the outer end of an actuating rod 17 of a pneumatic cylinder 18 that is mounted on the frame 1 and provides a means for effecting movement of the arcuated plates in a direction parallel with the axes of the rollers 7 and 11.
In the preferred embodiment the positioning elements 15 are formed integral with each arcuated plate with the drive mechanisms therefor consisting of separate pneumatic cylinders for each of said elements which are arranged so as to be simultaneously actuated. It should be understood, however, that the individual positioning elements could be operatively interconnected in a manner whereby they could be simultaneously actuated by a drive mechanism such as a single pneumatic cylinder. To prevent rotation of positioning element 15 and the arcuated plate about the axis of its cylinder 18, a guide rod 19 is provided which extends parallel to the actuating rod 17. This guide rod 19 has one end thereof fixed to the positioning element and extending from the latter it is freely slidable in an opening (not shown) provided in the support 3.
Referring now to FIGS. 2, 3 and 4 the method of applying an elastic band to a tubular workpiece by means of the apparatus described above first requires the manual placement of a workpiece 20 on the rollers 7 and 11 of the tension device 6 when the frame 1 is in loading position spaced from the sewing area of the machine. As is well known to those conversant in the art the sewing area is defined by the needle or needles 21 and the presser foot 22. The placement of the tubular workpiece must be such so that the portion depicted by numeral 23 is caused to engage the arcuate plates of the folding elements 16 and the semicircular blocks of the positioning elements 15. The next step is that of manually locating the elastic band 24 on the tubular workpiece so that it is positioned as shown in FIG. 3 between the rings 13 and the above-mentioned arcuated plates in a predetermined position that is characterized by a positioning member that defines a rounded rim 25 which among other things is effective in preventing the elastic band 24 from being displaced along the rollers as they are caused to rotate during the sewing cycle.
The minimal width of the rounded rim 25 is substantially the same as the width of the elastic band and it is preferable that the width of said rim be essentially equal to the minimal width of the elastic bands that are normally used.
At this point the portion of the workpiece intermediate the elastic band and the edge engaging the positioning elements 15 is automatically folded over said elastic band. This function is carried out by activating, by any suitable means not shown, the pneumatic cylinders 18 which together effect movement of the arcuated plates and positioning elements 15 toward and in a plane parallel with the axes of roller 7 and 11.
More specifically and as more clearly shown in FIG. 4, this movement of the arcuated plates causes that portion of the garment in contact with said plates to be folded over the elastic band.
This operation is also made possible by the fact that the elastic band is the element that maintains the workpiece in position on the rollers during movement of the arcuated plates.
The folding function described occurs along the entire edge of the tubular workpiece.
Upon completion of the folding function the arcuate plates are returned to their initial position, and the workpiece is then moved on the frame 1 into the sewing area beneath the presser foot 22 in order to be sewn. The frame 1 is adapted to move with the guides 5 from a loading position spaced from the machine to the sewing position. Obviously, the turning phase that takes place when the frame is moved towards the machine, as well as the displacement phase and also the starting or stopping of the machine, follows one after the other in an automatic cycle.
Although the present invention has been described in connection with a preferred embodiment it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and the appended claims.
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An apparatus for use with a sewing machine having a frame for supporting a tubular workpiece that is movable between a workpiece loading station and the sewing area of the machine. The workpiece is supported under tension on the frame which includes a positioning element for locating it thereon and a folding element for folding one of its ends over an elastic band placed on the workpiece at a predetermined distance from the positioning element. Movement of the frame to the sewing area places the workpiece in position to receive a seam of stitches in the folded portion within which the elastic band is located.
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This is a continuation of application Ser. No. 07/353,601, filed May 18, 1989, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to a telephone system and pertains, more particularly, to a telephone system that is adapted to allow outside calls and extension calls to be made through the same telephone line.
2. Background of the Invention
Related art telephone systems adapted to allow both outside calls and extension calls are of two different types, one using an exchange and the other using no exchange. The telephone system of the former type uses, for example, a private branch-exchange (PBX), a small private branch-exchange (small PBX), or a key system unit (KSU) of a key telephone system or the like.
An example of a multi-line telephone system (having two outside lines 1 and 2) using a related art small branch-exchange or key telephone system is shown in FIG. 3. As is shown, an exchange E is provided at the interface between the outside lines (1 and 2) and the extension lines (1 and 2), so that there is no direct connection of the outside lines and the extension lines. A large number of telephone units are commonly connected to the two extension lines 1 and 2. The exchange E functions to electrically separate the extension lines from the outside lines during extension calls.
An example of the telephone system of the type with no exchange is a telephone system which includes a channel used exclusively for extension calls in addition to the telephone lines. Typically, this exclusive extension communication channel is a power line, with inter-extension communication being performed by imposing a signal on the power line.
In all of the above-described related art, telephone systems which are either of the type which uses an exchange or of the type which does not use an exchange, only one communication could take place on a single telephone line at a time. Particularly, an outside call and an extension call could not occur simultaneously on one line. Further, since a sole communication channel is used both for outside and extension calls, it has been necessary, in the system using an exchange, to use the exchange at the interface between the extension line and the outside line so that the extension line is electrically isolated from the outside line during extension calls. Use of this exchange involves installation and wiring work therefore making the telephone system itself very expensive. In this system, furthermore, it has heretofore been impossible to simultaneously make an extension call and an outside call when the same telephone line is used for the making of these calls. Therefore, the number of simultaneous calls is limited by the number of lines.
On the other hand, the system which uses no exchange has had a problem in that a communication channel used exclusively for the extension had to be provided in addition to and separately from the ordinary telephone line. To avoid additional wiring in the typical installation, the existing indoor AC power line is frequently chosen as the means for providing this additional signal line for extension call purposes. A problem with using an existing indoor AC power line as the exclusive extension communication channel was that the quality of sound in communication was degraded due to various sources of noise such as microwave ovens, personal computers, televisions and the like, which are being used increasingly these days.
Accordingly, an object of the present invention is to provide an improved, simple and economical telephone system which enables outside calls and extension calls to take place simultaneously over the same telephone line without the necessity to employ an exchange or to provide additional communication lines.
Another object of the present invention is to provide an improved telephone system of the type disclosed herein which can also be implemented with a multiplicity of lines.
SUMMARY OF THE INVENTION
To accomplish the foregoing and other objects, features and advantages of the invention, the present invention provides an improved telephone system wherein an extension line is directly connected (i.e., without an intervening exchange) to an outside line and extension calls, preferably multiple extension calls, can be implemented simultaneously while an outside call is taking place between the extension line and the outside line during such extension calls.
To accomplish the above-described objects, the telephone system according to the present invention includes a common telephone line connected to an outside line, a plurality of telephone units connected to said common telephone line, an outside call circuit provided in each said telephone units for performing al the standard functions of a basic telephone instrument for use with said outside line. Each of the said telephone units also comprises an extension call circuit and a multiple extension call circuit for determining the composition and transmission level of signals transmitted to said common telephone line from said telephone unit depending upon whether the call is an extension call or an outside call. More particularly, the multiple extension call circuit embodied in this invention produces extension call signals which are higher in frequency than that of the outside calls and lower in level, whereby it enables extension calls and outside calls to take place simultaneously through the common telephone line.
Additionally, the telephone system according to the present invention also comprises an exchange control device provided in each of said telephone units for utilizing information from the phone line condition indicators, operator entered commands and a predetermined control program to control channel assignments and the output of the multiple extension call circuit. Said exchange control device includes logic circuitry, a keypad for operator entry, a predetermined control program and a digitally modulated command channel which is transmitted on the extension call channel simultaneously with extension calls.
BRIEF DESCRIPTION OF THE DRAWINGS
Numerous other objects, features and advantages of the invention should now become apparent upon reading the following detailed description in conjunction with the accompanying drawings, in which:
FIG. 1 is a block diagram showing the basic concept of a telephone system according to the present invention;
FIG. 2 is a view showing the general configuration of a multi-line telephone system which is an embodiment of the present invention;
FIG. 3 is a view showing the general configuration of a related art multi-line telephone system using a small private branch-exchange or a key telephone system;
FIG. 4 is a top view showing the appearance of a telephone unit for use in the telephone system of FIG. 2;
FIG. 5 shows the arrangement of FIGS. 5A and 5B;
FIGS. 5A and 5B form a circuit/block diagram of a master telephone unit;
FIG. 6 illustrates command formats;
FIG. 7 is a flow chart showing a flow sequence for making a call;
FIG. 8 is a flow chart showing a flow sequence for receiving a call from an outside line;
FIG. 9 is a flow chart showing a flow sequence for receiving a call from an extension line.
DESCRIPTION OF PREFERRED EMBODIMENTS
Reference is now made to the drawings herein, and, in particular, FIGS. 1-9, for further detailed explanation of the present invention. A basic configuration of the telephone system according to the present invention will now be described with reference to FIG. 1, which illustrates the concept of the system. In FIG. 1, only one of a plurality of telephone units connected to the telephone line is shown. It should be understood that the remaining telephone units have a construction identical or similar to the one illustrated. In the telephone system according to the present invention, as shown in FIG. 1, the telephone units are connected to the telephone line which is directly connected to the outside line or central office line, and each of the telephone units includes a device 3 for transmitting and receiving a speech signal, outside call circuit 4 of a type well known in the art which is capable of communicating said speech signal (as a base band signal) in a form suitable for transmission on the outside line, and a multiple extension call circuit 5 which is capable of communicating said speech signal as a carrier current signal. The transmitting/receiving device 3 can be, e.g., a standard telephone handset. More specifically, the base band signal is the original electrical analogue of the acoustic speech signal. The mentioned carrier current signal is a high frequency signal modulated by the base band signal, and superimposed on the telephone line, AC power line, optical fiber network or the like.
The telephone unit further includes switching devices 6A, 6B for selectively connecting the multiple extension call circuit 5 and the outside call circuit 4 to the telephone line, a switching device 7 configurable so that the speech signal transmitting and receiving device 3 is connected to the telephone line through the outside call circuit 4 during an outside call and to the telephone line through the multiple extension call circuit 5 during an extension call, and an extension call/outside call circuit switching control device 8 for applying a switching control signal to the switching devices 6A, 6B.
In order to allow simultaneous extension calls to occur, the multiple extension call circuit 5 includes a plurality of extension call communication channels which are different from the outside call communication channel. The telephone unit also includes an exchange control 9 which is connected to the telephone line through the multiple extension call circuit 5 and a command channel 11. The exchange control 9 controls the extension calls and the outside calls of this telephone system. This is accomplished by utilizing the command channel 11 which is separately implemented on the telephone line from the extension call channels (i.e., on a channel with a carrier frequency different from extension call channel frequencies). Further, at the time of making an extension call, the exchange control 9, together with the command channel means 11, generates a signal which designates one of said plurality of extension call communication channels to be used.
The extension call/outside call circuit switching control device 8 receives, as input, a signal from a ringer signal detecting device 13, a signal from an extension call/outside call designating device 15, a signal from on/off hook detecting device 17, and a signal from the exchange control 9, indicative of whether or not the receiving side of the extension is in a condition in which calls may be accepted.
The exchange control 9 receives as input a signal from the ringer signal detecting device 13, a signal from the on/off hook detecting device 17, and an extension number from extension number generating device 19 at the time of an extension call. As stated earlier, the exchange control 9 also receives exchange control signals from other telephone units, by way of the command channel 11 and the multiple extension call circuit 5. These inputs are used by the exchange control 9 to establish multiple extension calls on one or a plurality of telephone lines simultaneously with outside calls.
It is important to realize that the single line telephone system according to the present invention may be implemented as a multi-line telephone system when two or more outside lines are provided. In this case, two telephone lines are connected to these outside lines, respectively, and all of the plurality of telephone units may be selectably connected to both of the two telephone lines.
Now, with further reference to the drawings, the present invention is described in greater detail with respect to a multi-line telephone system which is an embodiment of the present invention.
FIG. 2 shows the general configuration of the multi-line telephone system 10 which has two outside lines 12 and 14 to which indoor extension lines 16 and 18, respectively, are directly connected (i.e., without an intervening exchange). Connected to both of these extension lines 16 and 18 through phone jacks 24, or any such conventionally well known means, are, for example, a master telephone unit 20 and, e.g., seven slave telephone units 22. In this embodiment, therefore, eight telephone units in total are directly connected to the outside lines without the intervention of conventional exchanges.
FIG. 4 shows a preferred appearance of a body 30 of the telephone unit 20 with the handset removed therefrom. The slave telephone units 22 have the same appearance as the telephone unit 20. The body 30 comprises a handset rest 32, a hook switch 34, telephone keys 36, an outside line label 38, outside line selector buttons 40, an internal communication intercom key 42, an extension number list 44, and internal communication accept inhibit (Don't Disturb) key 46, a hold key 48, and a dial pulse output/DMTF (tone) output selector key 50. In addition to these components, the body 30 may include a redial key 52, a pause key 54, a flash key 56, a monitor key 58, and a dialing indicator 60.
The circuit of the telephone unit 20 will now be described with reference to FIG. 5.
The circuit of the telephone unit 20 includes a bridge circuit 72 connected through an outside line switching relay 70 to each of the telephone extension lines 16 and 18, respectively. The bridge circuit serves to provide proper polarity, as required by the tone dialer 86. These extension lines 16 and 18 are in turn connected to outside telephone lines 12 and 14 respectively. These connections allow for the detection of ringer signals by conventional ringer detection circuitry 74 and 76, respectively.
The output of the bridge circuit 72 is connected to a speech network 82 through a mechanically or electrically operated hook switch 78 and a pulse dialer 80. The speech network 82 is connected to a handset 31 through an extension line/outside line switching relay 84. Connected to the speech network 82 is the output of a tone dialer 86. The extension call/outside call circuit 8 described above substantially comprises a tone dialer 86, speech network 82, a pulse dialer 80, a hook switch 78, and bridge circuit 72.
The handset 31 is connectable to the input of a channel FM modulator circuit 88 and the output of a channel FM demodulator circuit 90 through the extension line/outside line switching relay 84. The FM modulator circuit 88 and FM demodulation circuit 90 act to modulate and demodulate the carrier signals (used in extension communication) with analog signals from/to the handset 31. The FM modulator circuit 88 and the FM demodulator circuit 90 in the illustrated embodiment have four switchable carrier frequencies in the band of 280-400 KHz, and thus they have four communication channels CHO-CH3. Also, in this particular embodiment, the carrier frequency of each of these channels is selected to be 280 KHz for CHO, 320 KHz for CH1, 360 KBz for CH2, and 400 KHz for CH3, respectively. They constitute the plurality of extension call communication channels mentioned above.
Other conceivable embodiments could provide as many or more channels operating on the same or other frequencies without departing from the spirit and scope of the invention. Furthermore, other embodiments may utilize means of modulating said frequencies other than those described.
The output of the modulator circuit 88 and the input of the demodulator circuit 90 are connected to each of the telephone lines through a transformer 92 and an extension line switching relay 94. Capacitors 98 and 100 are connected between the extension line switching relay and each of the telephone lines for the purpose of isolating multiple extension call circuit signals of frequencies lower than the used carrier frequencies. In the preferred embodiment, the multiple extension call circuit 5, described above, substantially comprises the channel modulator circuit 88, channel demodulator circuit 90, and transformer 92, and an extension line/outside line switching device 8 controls the extension line/outside line switching relay 84, outside line switching relay 70 and extension line switching relay 94.
Connected to the transformer 92 is the output of an automatic exchange control comprising a command modulator circuit 102, a command demodulator circuit 104, a wave shaping circuit 106, a microcomputer 110, an array of LED indicators 112 and telephone keys 62. In the present embodiment the command modulator circuit 102 and demodulator circuit 104 operate on a carrier frequency of 430+2 KHz, which is different from the four carrier frequencies mentioned above. The input of the command modulator circuit 102 is connected to receive commands over line 103 and a carrier transmission on/off signal over line 105 from the microcomputer 110. The command modulator circuit 102 transforms the received command into an audio frequency signal and causes said audio frequency command signal to FM-modulate the command carrier frequency and transmit it during the period in which the carrier wave transmission is on. Other conceivable embodiments of the command signal could comprise any of several modulation means or carrier frequencies. The output of command demodulator circuit 104 is connected so as to provide commands originating from other telephone units connected in the telephone system comprising the present invention to the microcomputer 110 through wave form shaping circuit 106. The wave form shaping circuit 106 prevents outputs from the command demodulator circuit 104 which may result from noise disturbances reaching the system through the outside lines or 18 from causing a false command input to the microcomputer 110. A number of devices can be used as said wave form shaping circuit, including a bandpass filter and a low-pass filter. The characteristics of the wave form shaping circuit Will depend on the types of signals used as input to the microcomputer, as is well known in the art.
The microcomputer 110 may be a 4-bit microcomputer. It is preferably a type NEC PD75106G in this embodiment, although other logical signal processing means, including but not limited to discrete components, could be employed to provide the automatic exchange control contemplated by the present invention. The microcomputer 110, which includes associated memory for storing programmed instructions and call status information, etc., receives, as input information, a key output from keys 62 (schematically shown to represent the various keys of FIG. 5), ringer detection signals from the ringer detecting circuits 74 and 76, and commands from the command demodulator circuit 104 through the waveform shaping circuit 106. The keys 62 include the extension call/outside call designating device 15, extension number generating device 19, and the on/off hook detecting device 17, mentioned above.
The microcomputer 110 outputs, as control signals, an extension line/outside line switching signal to the relay 84 over line 111, an outside line switching signal to the relay 70 over line 113, and an extension line switching signal to switch the relay 94 using line 115. Further, the microcomputer 110 outputs CHO-CH3 selecting signals over lines 117, 119 to the channel modulator circuit 88 and demodulator circuit 90 and various commands to the command modulator circuit 102 over line 103 for the automatic exchange control. Additionally, the microcomputer 110 outputs signals to light-emitting diodes (LED) 112 for various display indications and also outputs dialer control signals to the pulse dialer 80 and the tone dialer 86 for transmission of the dialing signal over lines 121, 123, respectively.
Transmission levels of the channel modulator circuit 88 and the command modulator circuit 102 will now be described. According to the Technical Standard based on the provisions of the Public Telecommunication Law of Japan, when the transmission signal level in the normal frequency band up to 4 KHz is defined as P decibels above 1 milliwatt (dBm), other transmission levels above this frequency band are prescribed in relation to P dBm. In the frequency band 280 KHz to 432 KHz mentioned above, the other transmission level is prescribed to be P -60 dB or lower. Likewise, in the United States of America, Part 68 of the Rules of the Federal Communications Commission provides "the effective value (rms) of the line voltage component in the frequency range 270 KHz to 8 MHz, as averaged over 2 s, must not exceed -15 dBV" (decibels above 1 volt). Accordingly, the output level range of each of the modulator circuits 88 and 102 is adjusted to comply with these requirements for transmission levels.
Commands will now be described with reference to FIG. 6. Control information which is used for exchange control between a plurality of telephone units 20 to 22 is transmitted between these telephone units in the form of commands. These commands are classified in two types, that is, a first type of command, as shown in FIG. 6(a), comprising an operation code 91 only, and a second type of command, as shown in FIG. 6(b), comprising an operation code 93, a first operand 95, and a second operand 97.
An example of the first type of command is a ringer command. When a ringer signal arriving from an outside line is detected, such a ringer command is transmitted from a master telephone unit to all of the slave telephone units 22 to notify them of the presence of the call from the outside line.
Examples of the second type of command are an off-hook command, an extension-calling command, a hold command, a transfer command, and the like.
Such off-hook commands are generated when a receiver is taken off the hook in response to a call from the outside or an extension line or when connection of the line to the outside or to an extension line is to be signaled to the other telephone units. The operation code 93 has a code indicating the off-hook state. The first operand includes the number of the outside line (preferably numeral 1 or 2, indicating one of the two outside lines which is selected, e.g., by the outside line selector buttons 40 shown in FIG. 4) or the number of the extension line (preferably numeral 1 or 2). Whether the second operand 95 refers to an outside line or an extension line is determined by the operation code 93. The second operand 97 includes the identification number of any telephone unit from which the handset has been taken off-hook. Preferably, the identification number is one of the numerals 0-7 assigned to eight telephone units in all. As described above, all codes and operands are translated to or from an audio frequency by the command modulator/demodulator 102, 104 according to a predetermined code. The audio frequencies modulate the command carrier frequency 432 kHz.
The extension-calling command has an operation code indicative of the extension call and is generated by the caller when the internal communication key 42 is depressed to begin an extension call. In that case, the first operand contains the number (preferably numeral 1 or 2) indicating which of the two extension lines and which of the transmission (modulating) channel number (preferably numeral 0 through 3 indicating CHO-CH3) is to be used; and the second operand contains the extension number (preferably numeral 0 through 7) of the party being called. The extension line can be selected according to data input by the user from the keypad 62, or the extension line and/or the transmission channel can be selected by the microprocessor 110 according to a pre-stored program. A number of selection algorithms can be used. One such selection algorithm involves selecting the first non-busy line or channel in an ordered list (stored in memory) of line and channel numbers. Several methods can be used for ascertaining whether a line or channel is busy, including scanning the lines or channels for a busy signal or storing the busy/non-busy status of lines and channels in a table. The extension number of the party being called is derived from the data input through the keyboard 62.
The called-extension response command is generated by the called party in response to the extension-calling command, and its operation code has a code indicating whether the call is acceptable or not. Its first operand contains the number of the extension line and the number of the reception (demodulating) channel; and its second operand contains the extension number of the party called who responds to the call. The reception channel is selected by the microprocessor in the called-extension telephone in a manner similar to that described above in connection with selection of the transmission channel.
The hold command is generated by a telephone unit in which the hold key 48 is depressed during communication and is used, for example, during internal transfer of a telephone call. The operation code of the hold command has a code indicative of the hold state; its first operand contains the number of the extension line presently being used and the second operand contains the extension number of the telephone unit being placed in the hold state.
Following the operation of the hold key, the transfer command is then generated as a result of the transferor's receiver being on the hook after the extension number of the transferee has been entered using the keys 36 (see FIG. 4) and communication with the transferee has been established. Its operation code has a code indicating whether the transfer relates to an extension call or to an outside call. The first operand of the transfer operation code contains the number of the extension line; the second operand contains either the extension number of the transferor when transferring an extension call or the number of the outside line of the call to be transferred when transferring an outside call.
In addition to the transfer command described above, a dial switch command is provided which operates during an extension call to transfer the call from the currently used extension line to the other by means of the extension line switching relay 94. This dial switch command may be generated when an extension call is being conducted via a pair of telephone units and if an outside call is started via another telephone unit through the same extension line being used by that pair of units. For example, the dial switch command could be used when dialing pulses could interfere with the speech signal since the signal level of dialing pulses is very high in comparison to a low level modulated RF carrier which is conveying the extension call already in progress. Such a command, by diverting the dialing signals to another line simplifies the means necessary to provide adequate isolation between said dialing signals and extension calls in progress.
Operation of the telephone system according to the present invention will now be described with reference to the flow charts of FIGS. 7, 8 and 9.
FIG. 7 is a flow chart showing a sequence for the case in which each of the telephone units makes a call. First, in Step 200, the presence of an indication of internal communication is checked by detecting whether the intercom Key 42 see FIG. 4) has been depressed or not. In case of NO, the extension line/outside line switching relay 84 (see FIG. 5) is switched to the outside line in Step 202, and the outside line switching relay 70 (see FIG. 5) is switched to an idle line if necessary. In the next step 204, accessing of the party called is made by dialing, and thereafter this routine ends.
Returning now to Step 200, in case of YES, Step 206 follows where a check is made to determine whether or not all extension channels are busy.
In case of NO, indicating an extension call channel is available for use, then an extension call channel to be used, for example CHO, is selected in the next step 210. In step 212, the microcomputer outputs a signal for the generation of a dial tone, using, e.g., a tone generator (not shown), to indicate that it is in the state of allowing an extension call to be dialed. Next, a check is made at step 214 to determine whether or not the extension number has been entered at Key 62 (see FIG. 5). In the case of NO, the sequence loops to the Step 212. In case of YES, the sequence proceeds to step 216, in which an extension-calling command is transmitted. This command includes the number of the extension line and the number of the selected transmission modulating channel in the present example, CHO) in the first operand, and the extension number of the party being called (for example, in case of a call being made from the telephone unit 2 to the telephone unit 4, the extension number is 4) in the second operand. This command is transmitted to all of the telephone units.
Then, in Step 218, it is determined whether the telephone of the party being called is in the on-hook state or not by checking the called-extension-response command which is received from the party called. This coded response command, which is transmitted to all telephone units, indicates whether the called telephone is in the on-hook or off-hook state (in the operation code), the number of the extension line (in the first operand), and the extension number of the party called (for example, 4) in the second operand). By checking the operation code and the second operand, it can be ascertained whether the party being called has its telephone receiver on the hook or not. In the case of NO, the called extension is busy; therefore the sequence proceeds to Step 208 and this loop ends. In the case of YES, then in Step 220 the microcomputer outputs a signal to generate a ring back tone to notify the caller that the call has been placed.
In the next Step 222, presence of an off-hook command from the called party is checked. In case of NO, the sequence proceeds to Step 224, in which it is checked whether the caller replaced his receiver or not. This is determined from the status of switch 78, transmitted over line 125 (FIG. 5). In case of NO, the sequence is looped to the Step 220. In case of YES, this routine ends because the call was thereby terminated. In the Step 222, in case of YES, that is in case of receipt of an off-hook command, the sequence proceeds to the next Step 226. This off-hook command is described below in connection with FIG. 9, reference number 264, and includes the number of the extension line. The channel (for example, CH1 on which the called party will be transmitting (and on which, consequently, the calling party will be receiving or demodulating) is indicated in the first operand, and the extension number of the called party (for example, 4) is indicated in the second operand. In Step 226, a CHO selection signal (in the present example) is applied to the modulator circuit 88 (see FIG. 5) and, in the described example, a CH1 selection signal is applied to the demodulator circuit 90 (see FIG. 5), thus activating these circuits. This establishes the extension call circuit until either party places the handset on-hook and then this routine ends.
Next, sequences for the cases of receiving a call will be described with reference to FIGS. 8 and 9. The way in which an outside call is placed to the master telephone unit 20 (see FIG. 2) is the same as in the case of a conventional telephone unit and thus will not be described.
A call arriving from the outside line to the slave telephone unit 22 (see FIG. 2) will be described with reference to FIG. 8. In the first step 230, there is an input of a ringer command, that is, a call signal, to the slave telephone unit. In case of a call from the outside line, the call signal to the master telephone unit 20 is a ringer detection signal, but in the slave telephone unit 22 the call signal is a ringer command from the master telephone unit after the master telephone has detected the ringer signal.
In the next step 232, it is determined whether the slave telephone unit called is in the off-hook state or not. In case of YES, the line is busy and thus this routine ends. In case of NO, the sequence proceeds to Step 234 in which the microcomputer outputs a signal to generate a ringing tone and continues it until the off-hook state of the slave telephone unit called is detected in the next step 236. When the off-hook state is detected in the step 236, the extension line/outside line switching relay 84 (FIG. 5) is switched to the outside line in Step 238. Then, in Step 240, the outside line switching relay 70 (FIG. 5) is switched to the side which is ringing, and then this routine ends.
Next, description will be made of receiving a call from an extension line with reference to the flow chart of FIG. 9. In the first Step 250, there is an input of an extension-calling command. This is the command which was transmitted in the Step 216 o±FIG. In the next Step 252, the extension number (for example, 4) of the called party contained in the second operand of the command is checked to determine whether the slave telephone unit called is other than the unit originating the call. In the case of NO, this routine ends. In case of YES, it is determined in the next step 254 when the called unit is on the hook or not. In case of NO, that is, the called unit is off the hook, a called-extension-response command which has the operation code indicating the off-hook state is transmitted in Step 256, and then this routine ends. On the other hand, in case of YES, a called-extension-response command which has the operation code indicating the on-hook state is transmitted in Step 258. Then, in Step 260, a signal is output to generate a ringing tone, and this is continued until it is detected that the called telephone unit has been taken off the hook in Step 262. When the off-hook state is detected, an off-hook command is transmitted in Step 264. This command is the same command to be checked in Step 222 of FIG. 7. In the next Step 266, as before in Step 226 of FIG. 7, the modulator circuit 88 (at, e.g., CHO) and the demodulator circuit 90 (at, e.g., CH1) are activated by the selection signal from the microcomputer until either party places the handset on-hook. Then this routine ends.
While the present invention has been described with respect to a multi-line telephone system which is an embodiment of the invention, it may be modified as described below. While the above embodiment has been described as having the ringer only in the master telephone unit for the purpose of keeping costs low, it may alternatively be provided in the slave telephone units as occasion demands. In that case, the routine of FIG. 8 is unnecessary. Further, in the present invention, the modulation of extension channels can be performed not only with a frequency modulation techniques but also with an amplitude modulation technique or phase modulation technique. And yet further, the modulation means used to encode the command channel may be accomplished using a variety of digital modulation schemes including, but not limited to, frequency shift keying (FSK), phase shift keying (PCM), etc.
In the telephone system according to the present invention described hereinabove, the use of different signal levels enables an outside call or an extension call to be conducted from any telephone within the system connected to a common telephone line. Also by utilizing signal levels of an extension call channel different from those of the outside call channel and by suitable choice of modulating means an outside call and an extension call are allowed to take place on a common telephone line simultaneously. Further, the multiplexing of the extension call channels enables a plurality of extension calls to take place on a common telephone line simultaneously, limited only by the number of carrier channels provided.
According to the present invention, as described above, outside call communication and extension call communication using the same telephone line can be performed without using any exchange and yet without sacrificing sound quality.
Although the present invention has been described by way of a preferred embodiment, modifications and variations of the invention will be apparent to those skilled in the art, the scope of the claimed invention being described by the following claims.
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An improved telephone system in which a plurality of telephone units connected to a common telephone line is directly connected to an outside telephone line. Each telephone unit contains complete capability for making outside calls, for making extension calls, and for the automatic exchange control of the use of the common telephone line. This telephone system provides functions, including making multiple simultaneous calls on a single telephone line without requiring separate exchange equipment, additional extension or signal lines, or any sacrifice in signal quality. Furthermore, the telephone units in this system can be connected to more than one outside telephone line to expand the system capacity.
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RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Application Ser. Nos. 61/194,866 filed on Oct. 1, 2008; 61/211,579, filed on Apr. 1, 2009; and 61/273,308, filed on Aug. 3, 2009, the disclosures of which are each incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The invention relates to methods and catalysts for producing alcohols, ethers, and/or alkenes from alkanes. More particularly, the invention relates to a novel caged, or encapsulated, metal oxide catalysts and processes utilizing such catalysts. This invention further relates to a process to convert alkanes to alcohols and/or ethers to alkenes.
[0003] Lower alkenes, such as ethylene, propylene and butylene are used for a variety of applications. For example, ethylene is one of the most produced organic compound in the world, with the majority of ethylene being used to produce ethylene oxide, ethylene dichloride, and polyethylene. Lower alkenes may be recovered from petroleum by fractional distillation but demand far exceeds recovery by this method. Therefore, the majority of lower alkenes are produced by energy intensive cracking processes that are well known in the art. For example, ethylene is commonly produced in the petrochemical industry by steam cracking in which gaseous or light liquid hydrocarbons are heated to 700-950° C., in the presence of steam followed by rapid cooling, thereby converting large hydrocarbons into smaller ones and introducing unsaturation. Ethylene is then separated from the resulting product mixture by repeated compression and distillation. More recently, efforts to overcome the energy requirements and other issues, such as CO 2 issues, related to steam cracking, have resulted in processes involving catalytic cracking using a fluid-bed catalyst such as those processes described in U.S. Patent Publication No. 20090137857.
[0004] Other methods are known for producing alkenes, such as from acid dehydration of alcohols, are also well known. Such methods, however, have heretofore, only been practical in laboratory, and not industrial, settings and quantities. In such laboratory methods, alcohols may be formed by reaction of alkyl halides and metal hydroxides. For example, U.S. Pat. No. 5,334,777 shows the reaction of methyl chloride in the vapor phase with magnesium oxide and with magnesium oxide zeolite. U.S. Pat. No. 3,172,915 discloses the use of ferric oxide as a base to react with methyl chloride to form methyl alcohol, while U.S. Pat. No. 5,998,679 discloses a process in which ferric hydroxide is used as a base to react in the liquid phase with methyl bromide. Finally, U.S. Pat. Nos. 6,462,243; 6,465,696; 6,472,572; 6,486,368; 6,403,840; and 6,525,230 all disclose a process in which alkyl bromides are reacted with a metallic oxide to form alcohols and other products, such as di-methyl ether. All of these processes remain impractical for industrial use due mainly to catalyst attrition and over-halogenation problems resulting in the need for expensive re-crystallation.
[0005] There remains a need, therefore, for a process to form alcohol, ether or alkene at commercially practicable rates, with minimization or elimination of formation of other related compounds, and specially higher halides. There is a further need for catalysts to effectuate such process while minimizing or preventing the simultaneous production of higher halides during alcohol or alkene formation.
SUMMARY OF THE INVENTION
[0006] In one aspect of the invention provide a process to convert alkanes into alcohols and/or ethers including halogenating one or more alkanes with one or more halogens to form one or more alkane halides and one or more hydrogen halide acids; and reacting the alkane halides and hydrogen halide acid with one or more encapsulated metal oxide catalysts to form one or more compounds selected from the group of alkyl alcohols, ethers and alkenes and one or more metal halide; wherein the one or more encapsulated metal oxide catalysts comprises a pelletized and calcined mixture of an encapsulating material and an organic metal salt. In specific embodiments of the invention, the organic metal salt is selected from magnesium citrate and magnesium stearate. In certain embodiments, the encapsulating material is selected from bentonite, bauxite, and kaolin clays.
[0007] In another aspect of the invention, alkanes are further converted to alkenes by further conversion of the alcohols and/or ethers to alkenes by use of an appropriate catalyst. In some embodiments, the encapsulating material functions as a catalyst to convert alcohols and/or ethers to alkenes. In specific embodiments of the invention, the encapsulating material is process of claim 1 wherein the clay is bentonite.
[0008] In another aspect of the invention, a novel catalyst for the conversion of alkanes is provided wherein the catalyst is an encapsulated metal oxide. In certain embodiments of the invention, the encapsulating material is a clay having a pore size of 5 and 300 millimicrons, while in other embodiments, the pore size is between 10 and 100 millimicrons
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a schematic diagram of the one embodiment of the inventive process.
[0010] FIG. 2 is a schematic diagram of an alternative embodiment of the inventive process.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] Embodiments of the invention provide novel, highly effective encapsulated metal halide catalyst compositions for the formation of alcohols and alkenes.
[0012] In order that the invention be better understood the following equations illustrating the use of chlorine or bromine as the halide, magnesium as the active metal and magnesium chloride hydroxide or magnesium bromide hydroxide as the reacting base are shown:
Chlorination step
[0000] CH 4 ( g )+Cl 2 ( g )→CH 3 Cl( g )+HCl( g )
Alcohol formation
[0000] CH 3 Cl( g )+HCl( g )+2Mg(OH)Cl+3H 2 O( g )→CH 3 OH( g )+2MgCl 2 *2H 2 O
Chlorine and base Formation
[0000] 2MgCl 2 *2H 2 O+ 2 ( g )→2Mg(OH)Cl+Cl 2 ( g )+3H 2 O( g )
Alkene formation
[0000] 2CH 3 OH( g )→C 2 H 4 ( g )+2H 2 O( g )
The overall reaction is
[0000] 2CH 4 ( g )+O 2 ( g )→C 2 H 4 ( g )+2H 2 O
Bromination step
[0000] CH 4 ( g )+Br 2 ( g )→CH 3 Br( g )+HBr( g )
Alcohol formation
[0000] CH 3 Br( g )+HBr( g )+Mg(OH) 2 →MgBr 2 *H 2 O+CH 3 OH( g )
Bromine and hydroxide formation
[0000] MgBr 2 *H 2 O+1/2O 2 ( g )→Mg(OH) 2 +Br 2 ( g )
Alkene formation
[0000] 2CH 3 OH( g )C 2 H 4 ( g )+2H 2 O( g )
[0022] As previously discussed processes utilizing these reaction steps have heretofore been commercially impracticable because of attrition. Embodiments of the invention provide encapsulated metal oxide catalysts and processes using such novel catalysts to produce alcohols and alkenes from alkanes. In some embodiments of the invention, the material used to encapsulate the metal oxide catalyst may also function as a catalyst for the conversion of alcohols to alkenes. In certain embodiments of the present invention, one or more metal oxides are encapsulated in clay particles. The encapsulated metal oxide catalyst is produced by mixing one or more insoluble or slightly soluble high molecular volume organic metal salt with one or more porous materials, in a preferred embodiment, a clay material, including without limitation, kaolin, bentonite, and bauxite, and water to form a dough which is then pelletized, dried in air at typical room temperatures. The dried pellets are then heated in air to a temperature between 600° C. and 1000° C. to form a strong ceramic, porous pellet. Because the clay is annealed and hardened, it is important that the pore size be sufficiently large to house the metal halide hydrate, which is formed by exposure of the metal salt to water, without fracturing the clay structure. In preferred embodiments of the invention, the metal salt is a metal organic salt.
[0023] Alkanes useful in embodiments of the present invention include any alkanes having one or more carbon atoms. In a preferred embodiment, the alkane is methane. In other embodiments of the invention, the alkane feed includes more than one alkane.
[0024] The proportions of the organic metal salt to clay may vary from about 30 wt % clay to metal salt to clay to about 50 wt % metal salt to clay. The higher the proportion of clay to organic metal salt , the harder the pellet but the lower the capacity for alcohol production. The pellets can be made spherical or in any other shape, by hand or by machine techniques known in the art. Other types of clays may be used. The particle size may be any of the known particle sizes for known clays. In a preferred embodiment, the clay particle size is between 1 and 40 millimicrons.
[0025] Metals useful in embodiments of the invention may include any alkaline earth, alkali, basic or transition metal. Group 2 metals are preferred and zinc and magnesium are most preferred for use in the metal salt. Any halogen may be used to form the metal salt. Metal chlorides and bromides are used in preferred embodiments of the invention.
[0026] In a first preferred embodiment of the invention, the metal halide is magnesium chloride and in a second preferred embodiment the metal halide is magnesium bromide. In yet other embodiments of the invention the metal salt is zinc chloride or zinc bromide. In some embodiments of the invention, one or more metal halides are used wherein the metals may be the same or different metals and the halogen component may be the same or different halogens.
[0027] The weight proportion of the clay in the combined mixture of water, clay, and organic metal salt should be at least 30% by weight of clay. The weight percent of water may range from 20% to 30%. The weight percent of the organic metal salt may range from 50% to 70%. Without intending to be bound to any particular theory, it is believed that the clay particles in the mixture provide a highly porous material. For example, if magnesium citrate, having a molar volume of about 460 cubic centimeters per mole, is used as the organic metal salt, the pores left in the pellets formed from the mixture would be sufficient to accommodate the maximum size of the magnesium chloride hydrate, which is 130 cubic centimeters per mole for the hexa-hydrate MgCl 2 *6H 2 O. Thus, the clays used to produce the novel catalysts provide sufficiently large openings to accommodate the hexa-hydrate and not burst the clay structure. In a preferred embodiment of the invention, the pore size of the final ceramic clays is between 5 and 300 millimicrons. In a more preferred embodiment, the pore size is between 10 and 100 millimicrons.
[0028] Bentonite clay is a known catalyst for alkene formation from alcohols. Thus, when bentonite is used to encapsulate the metal halide hydrate, no additional activation agents are required to catalyze the formation of alkenes from alcohols. Other known clays and/or support structures are also known to catalyze the formation of alkenes from alcohols and the use of such supports and/or clays is within the scope of this invention. For example, montmonillonite, illite, chorite clays and certain phylosilicates also are known to catalyze the conversion of alcohols to alkenes and may be used as the encapsulating material in certain aspects of the invention. In embodiments of the invention utilizing kaolin and/or bauxite, additional activation agents or catalysts must be used to convert the alcohol into alkene.
[0029] In those embodiments of the invention in which the encapsulating material does not catalyze the conversion of alcohols to alkenes, or does not catalyze such conversion with adequate efficiency, small amounts, i.e., from 1 wt % to 10% and preferably about 2 wt % of finely ground X-type zeolite (also known as molecular sieves) in the acid form may be added to the mixture prior to formation of the dough and polarization. Alternatively, Y -type zeolite or an excess (i.e., over about 10%) of a finely ground X-type zeolite powder may be added to the mixture prior to formation of the dough and pelletization.
[0030] Halogenation of methane may be accomplished by means of any of a number of catalysts known in the art. However, industrially useful catalysts for methane halogenation include ultraviolet light and/or heat. Embodiments of the invention include the use of methyl halides, however produced or supplied. When temperature is used as a catalyst, the temperature for the methane halogenation step may range from 100° C. and 500° C., more preferably from 150° C. to 400° C. and most preferably from 250° C. to 350° C.
[0031] For formation of alcohol from the alkane halide utilizing the novel catalysts of the invention, the temperature is preferably between 120° C. and 200° C. but temperatures as low as 100° C. and as high 250° C. may be utilized. Likewise the alcohols may be converted to alkenes in the presence of the encapsulated metal oxide catalysts of the invention at similarly low temperatures, i.e., from between about 100° C. and 300° C., preferably between about 100° C. and 200° C. and most preferably between about 120° C. and 150° C.
[0032] FIG. 1 shows schematically one possible process equipment and materials flow for the inventive process. Referring to FIG. 1 , to form halide vapor, heated air is led from line 1 and opened valve 2 through line 3 and opened valve 4 to tubular reactor 5 . The tubes of tubular reactor 5 contain the inventive encapsulated metal halide. Halide vapor together with excess air leaves reactor 5 through opened valve 6 and is led through line 7 to condenser 8 where most of the alkyl halide is condensed and flows down to line 9 . Excess air and nitrogen containing traces of halide are led through line 8 a from condenser 8 to absorber 11 where the halide is absorbed and concentrated in an appropriate solvent down flowing through absorber 11 . Halide containing solvent flows downwardly through line 12 to stripper 13 where it meets a counter flow of methane coming through line 14 which strips the halide from the down flowing solvent. The halide-stripped solvent leaves stripper 13 through line 15 and is led through pump 16 to line 17 which feeds absorber 11 . Excess air and nitrogen are exhausted from absorber 11 trough line 18 .
[0033] Halide-enriched methane from striper 13 is led through line 19 to line 9 where it meets more halide coming from condenser 8 and together with re-circulated excess methane from line 20 is led into halogenating reactor 21 where they react at the proper temperatures to form methyl halide and hydro-halide acid. Reactor 21 works continuously while reactor 5 , 5 A, 5 B and 5 C operate batch wise. Reacted gasses from reactor 21 are led trough line 22 to cooler 23 A. Cooled gasses are led through line 24 to a series of reactors 5 , ( 5 A, 5 B, and 5 C not shown) one of which is in the metal basic form. Assuming reactor 5 is in the metal basic form the following procedure follows: Gasses containing methyl halide, hydro-halide acid and excess methane coming from line 24 are led through line 23 and opened valve 26 to reactor 5 , valve 6 being closed. Upward moving gasses through reactor 5 react with metal basic form to form ethylene, propylene etc., which together with excess methane are led through opened valve 27 and line 28 to separator 29 , where products are separated and delivered through product line 30 . Excess methane is led from separator 29 to line 14 , again to re-circulate in the system. Separator 29 can include compression, distillation, diffusion process equipment, as known in the art. Other standard equipment, well known in the art such as sampling ports, are not shown.
[0034] For continuous operation, besides the halogenation reactor there may preferably be four reactors containing the inventive encapsulated metal halide/metal halide hydroxide catalyst. In a first reactor the metal may be oxidized. These gasses in the second are being displaced with steam and cooled to the temperature of the ethylene reaction. The third reactor is treating the gasses to form alkenes and the forth reactor is being treated with steam to sweep out remaining gasses and also being heated to the oxidation temperature. Steam is also used to displace remaining gasses in the reactors to prevent possible explosions or contaminations.
[0035] If the encapsulated pellets are made spherical and prove strong enough they can be moved around in a system as shown in FIG. 2 .
[0036] Referring to FIG. 2 , methane is fed through line 4 to striper 5 , striping halide from halide solution coming down from striper 6 through line 7 . Methane with halide vapor from striper is led to saturation vessel 9 through line 8 where the balance of the required halide is added through line 10 . The resulting mixture of methane and halide is fed through line 11 to reactor 1 where methyl halide and through line 8 where the balance of the required halide is added through line 10 . The resulting mixture of methane and halide is fed through line 11 to reactor 1 where methyl halide and hydro-halide acid are produced. The methyl halide and hydro-halide acid are led through line 12 from reactor 1 to bottom of reactor 2 where they meet in countercurrent the magnesium base reacting to form a product gas containing methanol, di-methyl ether and ethylene which are exhausted from reactor 2 through line 13 . Metal halide formed in reactor 2 is led by gravity to lower reactor 3 through line 14 where it meets a counter flow of oxygen or air forming halide which together with excess oxygen or air are led through line 15 to cooler 16 where the halide condensed is led through line 10 to saturation vessel 9 .
[0037] Line 17 leads excess oxygen or air to striper 6 where it meets a countercurrent flow of solvent which strips halide from gasses which leaves striper 6 through line 18 to exhaust to the atmosphere. Solvent loaded with halide flows downwardly through line 7 to striper 5 . Spent solvent is led through line 19 to pump 20 which pumps solvent to striper 6 through line 21 . Oxygen or air is fed into reactor 3 through line 22 . Magnesium base produced in reactor 3 is led to ejector 23 through line 24 which is fed with air through line 25 and conveys the magnesium base through line 26 to cyclone 27 which empties the basic magnesium through line 28 to reactor 2 and exhausts air to the atmosphere through line 28 . Steam through line 29 into line 14 prevents gasses from reactor 2 to pass into reactor 3 . Steam through line 30 prevents gasses from cyclone 27 to pass into reactor 2 .
EXAMPLE 1
[0038] Highly porous encapsulated magnesium oxide catalyst of one embodiment of the invention can be made as follows 50 parts by weight of fine powder magnesium stearate Mg(C 18 H 35 O 2 ) 2 are well mixed with 50 parts by weight of fine powder bentonite and enough water added to form a doughy mixture which is then kneaded until smooth. The mixture is then pelletized and air dried at typical room temperatures. Once dried the pellets are calcined at to a minimum temperature of 600 degrees C. to form highly porous magnesium oxide, encapsulated in a ceramic clay matrix.
[0039] Highly porous encapsulated magnesium oxide can be made as follows 50 parts by weight of fine powder magnesium citrate, Mg(C 6 H 5 O 7 ) 2 —14H 2 O, are well mixed with 50 parts by weight of fine powder kaolin, 1 part by weight of ground X-type zeolite in the acid form and 50 parts by weight of water added to form a dough which is then kneaded till smooth and then pelletized and dried. Once dried the pellets are calcined to at least about 600° C. to form the magnesium oxide encapsulated in a matrix of hard clay or porcelain. The proportions of magnesium citrate to clay can vary. The higher the proportion of clay, the harder the pellet but the lower the capacity for halide or alcohol production, and thus, for alkene production. The pellets can be made spherical or in any other shape, by hand or machine, known in the art. Other types of clays and inorganic porous agglutinates, as are known in the art, may be used as the encapsulating material in embodiments of the invention.
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Methods and catalysts for producing alcohols, ethers, and/or alkenes from alkanes are provided. More particularly, novel caged, or encapsulated, metal oxide catalysts and processes utilizing such catalysts to convert alkanes to alcohols and/or ethers and to convert alcohols and/or ethers to alkenes are provided.
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This application is a division of application Ser. No. 08/919,371 filed Aug. 28, 1997, now U.S. Pat. No. 6,042,907.
The present invention is directed to sleeve labels for beverage containers, and more particularly to a method and system for coextruding an improved nultilayer sheet for such sleeve labels.
BACKGROUND AND OBJECTS OF THE INVENTION
U.S. Pat. No. 5,322,664 assigned to the assignee hereof, discloses a method and apparatus for making a clear single-layer non-foam polystyrene film for use as a sleeve label. A blend of crystal polystyrene containing no mineral oil and a block copolymer is extruded through an annular orifice and then stretched over a cooling mandrel. The film is stretched in both the machine direction and cross direction. The film may be formed into sleeves with the machine stretch direction oriented circumferentially, and then shrunk onto beverage containers.
It is well known that polyolefins, such as polyethylene and polypropylene, have better toughness and strength characteristics than polystyrene. However, polystyrene offers attributes superior to polyolefins in terms of stiffness and machinability. Efforts to overcome some of the limitations in properties of polyolefins, polypropylene in particular, have been to produce films or sheets with high levels of orientation in both machine and cross directions (biaxial orientation). Such techniques require substantial equipment investment and high capacity requirements.
Polystyrene is an amorphous material with excellent stiffness, cutting and machining qualities. It can be blended or polymerized with butadiene or other rubber-type modifying materials to increase its toughness and strength characteristics. It can also be extruded with a much lower equipment investment than biaxial orientation equipment for polypropylene. However, even by using undesirable amounts of liquid plasticizers or very expensive copolymers, the load force necessary to make polystyrene stretch exceeds values for polypropylene and values required in some market applications. One example where stretch under a low force is desirable is with label stock for PET carbonated beverage containers. Carbonated beverages are bottled at low temperature, around 50° F. Labels are applied to the containers either before or after filling with the beverage. These labels are wrapped around the containers in the machine direction axis of the sheet, with the ends being overlapped and bonded by a hot melt adhesive. As the beverage in the bottle warms to room temperature, the pressure created by carbonization makes the container expand, exerting a circumferential force on the container label. For example, a two liter bottle with carbonated content at typical carbonation levels can increase in diameter sufficiently to increase the circumferential dimension of the container 0.10 inches or more. The hot melt adhesives used in the beverage labeling industry are formulated for ease of processing, and typically do not possess high sheer strength at room temperature. It is therefore necessary that the label be such as to stretch at a lower force load than the sheer strength of the adhesive in order to accommodate expansion of the container without fracture at the label seam. This force load is typically less than four pounds. Label stock of high impact polystyrene typically require in excess of four pounds to stretch the required 0.10 inches.
Polyolefins and polystyrene, normally incompatible, can be made compatible by use of a compatibility agent, such as a styrene-ethylene/butylene-styrene block copolymer. However, processing problems created by the nature of the blends of amorphous polystyrene and crystalline polypropylene have resisted commercial applications of this technology. With a significant amount of polypropylene (above 40%) combined with polystyrene, the blend has a low melt strength that creates problems in extruding a sheet, particularly one that has a low caliper and is commercially economically viable. The presence of the polypropylene also makes the extruded sheet sensitive to a condition known as scaling (similar to fish scales), which is an appearance blemish visible as a chevron pattern with variable opacity.
It is therefore an object of the present invention to provide a multilayer sheet and method of manufacture adapted for use as a label sleeve on containers that combine the desirable properties of polyolefins in terms of toughness and strength, and the desirable properties of polystyrene in terms of stiffness and machinability. Another object of the present invention is to provide a system and method for coextruding a sheet film of polyolefin and polystyrene composition that are economical to implement, and that provide sleeve labels having the desirable properties described above. A further object of the present invention is to provide a container for carbonated beverages having a sleeve label in accordance with the present invention secured thereto.
SUMMARY OF THE INVENTION
A multilayer sheet in accordance with a presently preferred embodiment of the invention, which is particularly well adapted for use as a label sleeve on carbonated beverage containers, includes first and second coextruded unfoamed layers of polymer composition consisting essentially of polyolefin, polystyrene and a compatibility agent. The polyolefin and polystyrene are in a weight ratio in the range of about 30/70 to 70/30, and the compatibility agent is in the amount of about 5% to 10% by total weight. A pigment in the amount of about 10% to 15% by total weight may be included in one or both of the coextruded layers. The polyolefin preferably is selected from the group consisting of polypropylene, propylene/ethylene copolymers, propylene/butylene copolymers, propylene/ethylene/butylene copolymers and mixtures thereof, and the compatibility agent preferably comprises a styrene-ethylene/butylene-styrene block copolymer or a styrene-butadiene-styrene block copolymer. One of the unfoamed layers preferably is thicker and of higher strength than the other layer, while the other layer has a smooth uniform exterior surface.
The coextruded multilayer sheet preferably is fabricated by directing polymer material from first and second extrusion devices to an extrusion die in such a way that the polymer materials from the first and second extrusion devices exit the die as respective coextruded first and second layers of a composite sheet. Strength and appearance properties of the coextruded sheet are obtained by controlling temperature of the polymer materials as they enter the extrusion die such that the polymer material from one extrusion device enters the die at a different temperature from that entering the extrusion die from the other extrusion device. In particular, the polymer material is cooled at one extrusion device so as to enter the die at a lower temperature than the material from the other extrusion device. This lower temperature greatly enhances the strength characteristics of the resulting sheet. To obtain desirable appearance qualities in the resulting sheet, the coextruded first and second layers are cooled at different rates downstream of the extrusion die. In particular, the layer of material that was cooled prior to extrusion through the die is further cooled downstream of the die at a slower rate than the other layer.
In the preferred embodiment of the invention, the sheet is extruded through an annular extrusion die from which the layers exit as a composite conical film. Cooling air is directed onto the outer layer as the composite film exits the die, while cooling air is directed onto the inner layer at a position spaced downstream from the die in the direction of extrusion through the die. This delayed cooling of the inner layer after extrusion has been found to eliminate scaling in the inner layer. The extrusion process of the present invention preferably also includes stretching the film axially and circumferentially by pulling the film over a mandrel having a diameter greater than that of the extrusion die while cooling the mandrel to extract heat from the film. The film is cut diametrically downstream of the cooling mandrel and wound into coils of sheet material for further processing.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention, together with additional objects, features and advantages thereof, will be best understood from the following description, the appended claims and the accompanying drawings in which:
FIG. 1 is a schematic diagram of a system for coextruding a multilayer sheet in accordance with a presently preferred embodiment of the invention;
FIG. 2 is a sectional view on an enlarged scale of a portion of the system illustrated in FIG. 1;
FIG. 3 is a sectional view taken substantially along the line 3 — 3 in FIG. 2;
FIG. 4 is a perspective view of a multilayer sheet formed in accordance with the present invention;
FIG. 5 is a graph that illustrates a characteristic of the present invention;
FIG. 6 is an elevational view of a carbonated beverage container in accordance with a presently preferred implementation of the invention; and
FIG. 7 is a fragmentary view on an enlarged scale of the portion of FIG. 6 within the circle 7 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates a system 10 for forming a multilayer sheet adapted for use as a label sleeve on a container in accordance with a presently preferred embodiment of the invention. A first mixing extruder 12 receives material from a hopper 14 for melting and mixing the material, and directing the material at elevated temperature to a cooling extruder 16 . A second or satellite extruder 18 has a hopper 19 for receiving raw material to be extruded, and feeds extrudate at elevated temperature to an annular coextrusion die 20 . The extrudate streams are directed through die 20 in such a way that the material from extruders 12 , 16 forms an inner layer and the material from extruder 18 forms an outer layer of the extrudate 21 that flows through die 20 .
An air ring 22 (FIG. 2) is disposed at the outlet of annular die 20 for directing cooling air onto the outer layer of the annular film 21 as the film exits die 20 . The film is pulled by nip rolls 23 from die 20 over a cooling mandrel 24 (FIGS. 2 and 3) in such a way that the film is stretched both axially in a machine direction and circumferentially in a cross direction as the film flows from die 20 to mandrel 24 . An inner air ring 26 is mounted on a shaft 28 that extends from mandrel 24 , and is spaced from the end of die 20 by a spacer 30 . Ring 26 receives cooling air, and directs the cooling air radially outwardly against the inner layer of film 21 at a position, determined by spacer 30 , downstream from die 20 and outer ring 22 . A circumferential array of passages 32 extend axially through mandrel 24 for passage of the air from ring 26 so that film 21 does not expand or balloon from air pressure. A passage 34 in mandrel 24 also provides for water-cooling of the mandrel. Downstream from mandrel 24 , there is disposed a cutter knife 36 for cutting film 21 diametrically across the film. From knife 36 , the separated film strips extend to nip rolls 23 , and thence to winders 38 , 40 for coiling the separated sheet into separate coils.
The material components of the desired polymer formulation are mixed and fed to extruders 12 , 18 by means of hoppers 14 , 19 . The rates of flow at extruder pair 12 , 14 and at extruder 18 are selected so as to provide the desired layer thicknesses at film 21 (FIGS. 1, 2 and 4 ). As noted above, the extrudate from extruder pair 12 , 14 forms the inner layer 42 of the multilayer film 21 , while the material from extruder 18 forms the outer layer 44 . Film 21 forms a frustroconical shape as it emerges from annular die 20 and is drawn over the mandrel. Annular ring 22 closely adjacent to the extruder die provides immediate cooling air flow to the outer layer of the tubular web as it emerges from the die. Suitable controls for volume and temperature are used for the forced air cooling. Inner ring 26 applies controlled volume and temperature forced air cooling downstream from the die face. Mandrel 24 is plated with nickel/chrome and is highly polished. This slick smooth surface improves the surface of the film produced and contributes to control of web tension between the mandrel and pull nip rolls 23 . In one implementation of the present invention, extruder 12 comprises a 4½ inch (30:1) extruder, while extruder 16 comprises a 6 inch (24:1) secondary cooling extruder. Satellite extruder 18 is a 2½ inch (24:1) extruder. Die 20 is a 16¼ inch coextrusion two-layer annular rotary die, while mandrel 24 is a 28½ inch cooling mandrel with a high finish smooth nickel/chrome surface. Inner ring 26 is located 5¼ inches downstream from the face of die 20 , and the cooling water applied to mandrel 24 is maintained at 160° F. The mandrel and die are sized to provide a stretch ratio (die diameter to mandrel diameter) of 1.75.
Extruder 16 is employed strictly to cool the melt from extruder 12 , which will increase its strength. In one implementation of the invention, the melt from extruder 12 is at about 425° F., and is cooled to about 325° F. during passage through extruder 16 to die 20 . While this cooling increases melt strength, it also has some negative effects on smoothness and appearance of the formed sheet. The second thin layer from extruder 18 is coextruded on the outside of the tubular film, and has a melt temperature of about 400° F. as it exits extruder 18 to die 20 . This preferred temperature differential was arrived at by trial and error employing the specific materials hereinafter described. Other temperature differentials may be suitable for other materials. The cooled inner layer with increased melt strength provides support for the hot thin outer layer. By extruding the outer layer at elevated temperature, it develops the desire properties of gloss and smoothness with uniform appearance over the surface of the precooled inner layer.
It has also been found that further cooling of the precooled inner layer must be accomplished at a slower rate after exit from extrusion die 20 , as compared with rapid cooling of the outer layer by ring 22 . This lower cooling rate for the inner layer helps prevent scaling at the inner layer. Air ring 26 and mandrel 24 are closely axially aligned with extrusion die 20 . In this way, air ring 26 is centered and equidistant from web 21 in total circumference. This also accomplishes the objective of providing a slower cooling rate for the inner layer due to being further away from the material than if air ring 26 were mounted on the opposing face of die 20 , as is typical in the prior art. The leading or nose portion of mandrel 24 has a slight taper so that film 21 contacts the mandrel at a smaller diameter than the body of the mandrel. This helps ensure that the material will make intimate contact over the outer diameter of the mandrel, which then creates the tension needed between the mandrel and the pull nip rolls for achieving the desired amount of stretch in the axial or machine direction. Changes in the temperature of the mandrel, by means of controlling temperature of water flowing through cooling passages 34 , can be used to increase or decrease this web tension. Lower temperatures increase tension while higher temperatures decrease tension.
A number of tests have been run in implementation of the invention. In these tests, the rate of flow through extruders 12 , 16 , 18 were such as to provide a total material thickness of about 1.5 to 2.5 mils. It is preferred that the thickness of the inner layer be two to eight times the thickness of the outer layer. It is considered preferable to maintain layer 44 at a thickness of about 0.2 to 0.3 mil. A currently preferred construction has an inner layer 42 of about 1.2 mils thickness and outer layer 44 of about 0.3 mils thickness. The following materials were used: (1) Shell Chemical Co. DS6D82 —a propylene/ethylene copolymer having a melt flow rate of 7.0 gms./10 min. and a melting point (by DSC) of 136° C.; (2) Huntsman Chemical Co. 203—a general purpose polystyrene having a melt flow rate of 8.0 (condition G); (3) Shell Chemical Co. Kraton 1657—a linear styrene-ethylene/butylene-styrene block copolymer having a styrene-to-rubber ratio of 13 to 87 (Kraton D1102 would be a suitable triblock styrene-butadiene-styrene block copolymer compatibility agent, and Kraton D1184 would be a suitable radial styrene-butadiene-styrene block copolymer compatibility agent); and (4) O'Neil TiO 2 white concentrate containing 60% TiO 2 and 40% polystyrene. Formulations have been extruded varying the weight ratio of polystyrene to polypropylene/polyethylene from 30/70 through 40/60, 50/50, 60/40 to 70/30. To these blends, the Kraton compatibility agent was varied from 5% to 10% by total weight, and the pigment concentration from 10% to 15% by weight.
Physical property data are shown in Table I for the blend of 50/50 polystyrene to propylene/ethylene copolymer containing 10% compatibility agent and 15% pigment concentration, with comparison data for a commercial grade polystyrene sheet and a biaxially oriented polypropylene sheet. These sheets are low gauge film-like materials suitable for use as substrates in laminated structures with clear polypropylene film for the carbonated beverage market.
TABLE I
Physical Properties Unlaminated Substrate
Polystyrene
PS/PP Blend
Polypropylene
Caliper (mils)
1.6
1.7
1.3
Density (PCF)
52
49
42
MD* Yield (PSI)
6311
4040
2770
MD Elongation (%)
29
45
97
MD Break (PSI)
5760
5340
9439
MD Modulus (PSI × 10 5 )
2.6
1.6
0.2
MD Stiffness (MGS)
4.6
3.8
2.4
CD* Yield (PSI)
3290
1500
13580
CD Elongation (%)
35
18
23
CD Break (PSI)
3360
1470
17920
CD Modulus (PSI × 10 5 )
2.3
0.9
0.2
CD Stiffness (MGS)
2.2
1.8
4.0
CD Tear (Lbs.)
3.8
3.8
8.1
*Machine Direction,
**Cross Direction
In comparing this data, it is important to recognize that the polypropylene sheet is strongly biaxially oriented, with the greater orientation being in the cross direction. The polystyrene sheet and the polystyrene/polypropylene blend sheet of the present invention were made without special tentering frame orientation (machine direction and cross direction stretching) equipment. Since a container label is typically wrapped with the machine direction orientation circumferentially around the container, the machine direction orientation is the more critical property requirement. As can be seen from the data of Table I, the following properties of the polystyrene/polypropylene blend materials of the present invention fall between those of the polystyrene and polypropylene: MD yield, MD elongation, MD tinsel brake and MD tensile modulus. The data thus shows that the polystyrene and polypropylene have individually affected the final properties of the polystyrene/polypropylene blend materials of the invention, and that the material of the invention has assumed attributes of both the polystyrene and polypropylene. A currently preferred sheet construction has a layer 42 of 60% polystyrene and 40% polypropylene (with compatibility agent) and a layer 44 of 70% polystyrene and 30% polypropylene (with compatibility agent). Thus, the sheet compositions need not be identical, although a radical difference in composition could result in curling.
Referring to FIGS. 6 and 7, the preferred form or structure of a beverage label is for the opaque two-layer substrate 42 , 44 of the present invention to be adhesively laminated with a thin clear biaxially oriented polypropylene film 46 , with a printed design affixed to the inside, and an adhesive layer 48 sandwiched between layers 46 , 44 . The thin gauge oriented polypropylene film 46 provides high gloss and a protective layer over the printed layer 48 to prevent scuffing or abrasion of the inks. In recycling the labeled PET bottles 50 after use, the bottles and labels are ground up together and exposed to a rinse cycle. With the laminated structure illustrated in FIG. 7, the inks in layer 48 are still protected from chemical attack by the rinse solution, and the label material can be separated from the bottle material to be salvaged without ink color contamination of the bottle material. Listed below in Table II are physical properties of the three substrates shown in Table I after adhesive lamination with a seventy gauge clear biaxially oriented polypropylene film 46 :
TABLE II
Physical Properties Laminated Structures
Property
Polystyrene
PS/PP Blend
Polypropylene
Caliper (mils)
2.3
2.4
2.0
Density (PCF)
55.3
53.6
46.0
MD Yield (PSI)
6389
4951
3880
MD Elongation (%)
59
79
124
MD Break (PSI)
8496
9435
12550
MD Modulus
2.9
2.4
2.4
(PSI × 10 × 10 5 )
MD Stiffness (MGS)
14.5
15.6
7.4
CD Tear (Lbs)
11.2
16.2
17.9
The data in Table II show that the polystyrene/polypropylene blend material of the present invention has produced a laminated sheet having the beneficial qualities of both polystyrene and polypropylene, while reducing the negative performance aspects of each. This may be further demonstrated by a test closely related to the label performance on a carbonated beverage container, which slowly expands in diameter as the beverage warms from about 50° F. to room temperature as typical in the beverage industry. Sample strips 0.5 inches wide of each of the three label materials were stretched 0.10 inches on a standard Instron tensile tester at a speed of 0.02 inches/minute. The force necessary to obtain the 0.10 inch elongation was recorded. The samples were held in stretched condition for 10 minutes, with the force (strain) recorded each minute. FIG. 5 is a graph that shows the results on the three different types of label specimens. As can be seen, the force data for the label material prepared with a substrate from the polystyrene/polypropylene blend of the present invention falls approximately half way between the polystyrene and the polypropylene samples. One objective of this invention was to develop a material which would stretch at a lower force value than possible with polystyrene, but would not be subject to stretching at the low force values demonstrated for polypropylene. The polystyrene/polypropylene blend prepared in accordance with the present invention clearly accomplishes this objective. The invention therefore provides a multilayer sheet material adapted for use as a label sleeve on containers, as well as a method and apparatus for forming such sheet and a label formed therefrom, that combines the attributes of both polystyrene and polypropylene while eliminating the negative features inherent in these individual materials, resulting in a label material for carbonated beverage containers that is superior in performance to labels made from either polystyrene or polypropylene alone.
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A multilayer sheet, which is particularly well adapted for use as as a label sleeve on carbonated beverage containers, includes first and second coextruded unfoamed layers of polymer compositions each consisting essentially of polyolefin, polystyrene and a compatibility agent. The polyolefin and polystyrene are in a weight ratio in the range of about 30/70 to 70/30, and the compatibility agent is in the amount of about 5% to 10% by total weight. A pigment in the amount of about 10% to 15% by total weight may be included in one or both of the coextruded layers. The polyolefin preferably is selected from the group consisting of polypropylene, polyethylene and mixtures thereof, and the compatibility agent preferably comprises a styrene-ethylene/butylene-styrene block copolymer. One of the unfoamed layers preferably is thicker and of higher strength than the other layer, while the other layer has a smooth uniform exterior surface.
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[0001] This application claims the benefit under 35 U.S.C.119(e) of U.S. provisional application Ser. No. 60/808,978, filed May 30, 2006.
FIELD OF THE INVENTION
[0002] The present invention relates to a system for dehumidifying and more particularly relates to a system for dehumidifying enclosed spaces, for example crawlspaces or attics in buildings and the like.
BACKGROUND
[0003] In various enclosed spaces, in building and the like excessive moisture build-up or humidity in the air can cause undesirable growths of mold, bacteria or various undesirable microbes. Accordingly it is desirable to remove moisture from such enclosed building spaces.
[0004] Small stand alone units are known for dehumidifying in which a dehumidistat, a fan for circulating air and coils of a condenser and evaporator cycle are provided on a common housing, however, such units typically have a limited capacity to remove moisture, are ineffective at circulating air through a large space, and have no on-going monitoring ability.
[0005] U.S. Pat. No. 6,826,920 belonging to Wacker and US Application Publication No. 2006/0086112 belonging to Bloemer et al each disclose systems for controlling humidity, however neither includes its own fan, but rather requires operation in conjunction with the air handler of an HVAC environmental control system of the building.
[0006] US Application Publication No. 2005/0005616 belonging to Bates et al discloses a fungus abatement system for a lower enclosed space in a building. The system is an open loop system which draws air from the space at plural locations and exhausts the air externally from the building. Such a system is not well suited for use in colder environments due to the resulting heat loss of repeatedly exhausting air which is heated in the space by convection or conduction. Furthermore, the system is not effective for dehumidification in environments where the air drawn back into the space is also humid.
SUMMARY OF THE INVENTION
[0007] According to one aspect of the invention there is provided a dehumidifying system for dehumidifying a space of a building, the system comprising:
[0008] a dehumidifier unit comprising an evaporator coil, a condenser coil, and a compressor arranged for circulating heat exchanger fluid through the coils;
[0009] ducting arranged for communicating from the space to an inlet of the dehumidifier unit and for communicating from an outlet of the dehumidifier unit to the space;
[0010] a fan arranged for circulating air through the ducting between the space and the dehumidifier unit;
[0011] a dehumidistat arranged for communication with airflow from the space to the dehumidifier unit to measure a humidity level of air in the space, the dehumidistat having a set point humidity level and being arranged for activating the dehumidifier unit responsive to the humidity level in the space exceeding the set point humidity level.
[0012] By providing a system in which ducting communicates a dehumidifier unit to a space to be dehumidified, a fan can circulate the air thoroughly throughout the space in a closed loop configuration with the space so that all humid air can be brought into contact with the dehumidifier unit for dehumidification. Supporting the dehumidistat in communication with the air being circulated ensures that the system operates in the most efficient manner.
[0013] When the system is provided in combination with a building including a controlled space in communication with an air handler of an environmental control system of the controlled space and an uncontrolled space, the ducting is preferably arranged in communication with the uncontrolled space independently of the air handler. The dehumidifying system is thus well suited as an add-on to a building already having an HVAC system in which the dehumidifying system communicates with a crawlspace or basement area independently of the HVAC system.
[0014] The dehumidifier unit may be supported in the controlled space of the building and arranged to communicate with the uncontrolled space of the building.
[0015] There may be provided a single common intake arranged to be supported centrally in the space, the ducting communicating between the common intake and the inlet of the dehumidifier unit.
[0016] Furthermore, there may be provided a distributed outlet arranged to be supported in the space for communication with the space at a plurality of positions spaced generally about a periphery of the space, the ducting communicating between the outlet of the dehumidifier and the distributed outlet. The distributed outlet acts as a manifold to ensure that dried air, from which the dehumidifier has removed moisture, is thoroughly spread through the space to be dehumidified. Accordingly a greater amount of moisture remaining in the space can be collected by the drier air and drawn towards the common intake which is preferably centrally located in relation to the peripherally distributed outlet.
[0017] The inlet and the outlet of the dehumidifier are preferably arranged to communicate with the space in a closed loop configuration.
[0018] Both the fan and the compressor may be operated simultaneously responsive to the dehumidistat and a timer.
[0019] The fan may also be responsive to a timer to circulate air periodically through the space independently of the operation of the dehumidifier unit to ensure accurate moisture determination by the dehumidistat.
[0020] In some instances, both the fan and the compressor may be responsive to a timer to periodically circulate and dehumidify air within the space.
[0021] There may also be provided a heater for heating the space, which is preferably coupled in series with the ducting for heating air circulated therethrough.
[0022] The heater may be in communication between the space and the inlet of the dehumidifier unit in some instances. Pre-heating the air entering the de-humidifier unit increases the resistance to ice formation on the evaporator coils to ensure continued efficient operation of the de-humidifier unit.
[0023] In other instances the heater may be in communication between the outlet of the dehumidifier unit and the space. In this instance, the heated air is arranged to collect a larger amount of moisture from the space prior to re-entering the dehumidifier unit where the moisture is collected.
[0024] The heater may be responsive to a thermostat supported within the space or responsive to a flow of air through the ducting.
[0025] There may be provided a de-icing mechanism coupled to the evaporator coil and arranged for selectively heating the evaporator coil such that ice is arranged to be removed from the evaporator coil.
[0026] The space may be provided in combination with an enclosed and unheated space within a building, comprising for example a crawlspace of the building.
[0027] When the building includes a plumbing drain, the dehumidifier unit may include a drain arranged to drain condensate from the evaporator coil directly to the existing plumbing drain of the building.
[0028] One embodiment of the invention will now be described in conjunction with the accompanying drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is a schematic view of the system installed for communication with the crawl space of a building.
[0030] FIG. 2 is an enlarged schematic view of the ducting communicating between the dehumidifier unit and the space to be dehumidified.
[0031] In the drawings like characters of reference indicate corresponding parts in the different figures.
DETAILED DESCRIPTION
[0032] Referring to the accompanying figures there is illustrated a dehumidifier system generally indicated by reference character D. The dehumidifier system D is particularly suited for communication with an enclosed space, which may be heated or unheated, for example a crawl space 8 below a building 16 .
[0033] In a typical installation, the system D is installed independently of an HVAC system of a building including a controlled space in communication with an air handler of HVAC environmental control system. The system D is particularly suited to being in communication with an uncontrolled space of the building which does not communicate with the HVAC system.
[0034] The system includes a dehumidifier unit supported within a suitable housing 14 or container within which various operating components for dehumidification are supported. The housing 14 of the dehumidifier unit is supported in the controlled space of the building and is arranged to communicate with the uncontrolled space of the building through suitable ducting in communication with the uncontrolled space independently of the air handler. Both of the uncontrolled and controlled spaces typically comprise an enclosed space.
[0035] Within the housing there is provided a de-icing coil 1 which serves to melt any ice built up on an evaporator 2 also supporting within the housing. The evaporator 2 serves to condense moisture in the air which passes thereacross by absorbing heat from the moisture in the air which causes heat exchanger fluid within coils of the evaporator to be evaporated.
[0036] Coils of the evaporator 2 communicate in series with a condenser 3 which serves to condense the heat exchanger fluid therein in a second phase of the heat exchanger cycle. Also within the housing is a compressor 4 which serves to compress the heat exchanger gas for circulating the heat exchanger fluid through the evaporator and condenser. The operation of the dehumidifier unit alone operates generally according to traditional and conventional refrigeration techniques.
[0037] The housing also includes a fan 5 which serves to circulate air through the housing of the dehumidifier unit by both drawing air from the space and returning dehumidified air back to the space.
[0038] The ducting includes a supply air duct 6 which communicates from an outlet of the dehumidifier unit to a series of air distribution ducts 15 to supply dehumidified air from the unit at the fan outlet back into the space of air to be dehumidified. The ducts 15 comprise distributed manifold outlet arranged to be supported in the space for communication with the space at a plurality of positions spaced from one another generally about a periphery of the space. The dried air from the dehumidifier is thus directed into all areas of the space to collect moisture evenly from the space.
[0039] The ducting further includes a return air duct 7 which includes an inlet located within the space which draws humid air from the space and communicates this humid air to the inlet of the dehumidifier unit. An air filter 12 is mounted in the space, in series with the airflow from the space to the unit, at the inlet end of the return air duct which returns air from the space to the dehumidifier unit. The inlet within the space comprises a single common intake arranged to be supported in the space at a central location to be generally evenly spaced from the spaced positions of the distributed outlet 15 . This further ensures that moisture is evenly collected from the space.
[0040] A heater 9 A is mounted in series with the supply air duct 6 so that the dehumidified air can be heated prior to being returned into the space to be dehumidified. The heater comprises an electrical resistance heater which is activated responsive only to a flow of air through the supply air duct. The heater 9 A is controlled by a thermostat 11 which is supported within the enclosed space 8 to be dehumidified for operating the heater only when temperature in the space falls below a prescribed set point of the thermostat 11 .
[0041] Optionally, a heater 9 B is mounted in series with the return air duct 7 which directs air to the inlet of the dehumidifier unit. The heater 9 B is located within the controlled space 1 6 A, separate from, but close to the inlet of the dehumidifier unit. The heater 9 B in the duct 7 leading to the dehumidifier unit serves to prevent freezing up of condensate on the coils of the evaporator 2 . The heaters 9 A and 9 B can be used in the same embodiment or independently of one another in different embodiments of the invention.
[0042] Operation of the dehumidifier unit is responsive to both a timer 10 supported on the unit and a dehumidistat 13 which measures a level of humidity in the surrounding air. The dehumidistat 13 is supported in communication with airflow from the space to the unit, for example centrally within the space 8 , where air is circulated to optimize the reading of the humidity level. The dehumidistat 13 has a set point humidity level which can be set at an adjustable level as the user or installer desires. Whenever the level of humidity exceeds the set point humidity level, the dehumidistat signals the dehumidifier unit to operate both the compressor and the fan together for both circulating air and dehumidifying the air being circulated in a single operation.
[0043] The dehumidistat 13 may comprise two separate controls designated as a winter controller and a summer controller or a single dual function controller. In each instance, the dehumidistat 13 is operable in a winter mode in which the dehumidistat is operable relative to a winter set point and a summer mode in which the dehumidistat is operable relative to a summer set point. The winter and summer set points comprise different moisture level set points which represent different recommended moisture levels depending upon different seasons.
[0044] The timer 10 is set to also operate the compressor and fan together at periodic intervals, for instance once or twice a day, to maintain proper circulation of air through the enclosed space 8 . Once the timer begins operation for a prescribed period of time, if the circulated air is detected by the dehumidistat to be too humid, continued operation of the dehumidifier unit results. Alternatively if after some initial period of operation responsive to the timer, the dehumidistat detects that the humidity level is below the set point humidity level, continued operation of the dehumidifier unit can be ceased which will in turn cease operation of the heater as a result of the discontinued airflow through the ducting.
[0045] As described herein, when the system operates and is turned on, the system provides air circulation through the area where it is intended. As the air and moisture pass through the air handler, the moisture is captured at the evaporator and sent out by a direct connection to a corresponding drain of the building. When the moisture level reaches a dehumidistat set point, the entire system shuts down. Periodically the system will turn itself on by way of a programmable timer to sample the moisture content in the air, and depending on the moisture level in relation to the dehumidistat set point, the system either continues running or shuts off. In addition to the timer, the dehumidistat also activates the system when the humidity in the space area exceeds the set point of the dehumidistat. The system is particularly suited for use in crawl spaces of houses and building or any other confined spaces where moisture level needs to be monitored and controlled. The system will be available through a range of sizes from very small units to very large units to accommodate a corresponding range of enclosed spaces which may also vary in size.
[0046] Since various modifications can be made in my invention as herein above described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without department from such spirit and scope, it is intended that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
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A system dehumidifies a non-environmentally controlled, enclosed space of a building, for example a crawlspace, using a dehumidifier unit comprising an evaporator coil, a condenser coil, and a compressor arranged for circulating heat exchanger fluid through the coils. A fan operates in series with closed loop ducting to communicate air from the space to the dehumidifier unit and back to the space independently of an HVAC system of the building. The fan and dehumidifier unit are responsive to a dehumidistat. A distributed outlet distributes air from the unit to peripheral positions about the space. A heater is coupled in series with the ducting for heating air circulated therethrough.
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BACKGROUND
[0001] The present invention relates to preserving perishable products in a display case.
SUMMARY
[0002] In one embodiment, the invention provides a display assembly for containing and displaying perishable products. The display assembly includes a case having at least one wall and defining an internal volume, a quantity of gas contained in the case, the gas including ethylene emitted from the perishable products, and an electro hydrodynamic thrust device positioned in the case. The electro hydrodynamic thrust device ionizes a portion of the quantity of gas. The ionized gas includes at least one reactive oxygen species, and the at least one reactive oxygen species reacts with the ethylene to break down the ethylene.
[0003] In another embodiment the invention provides a method of retrofitting a display case for displaying perishable food. The method includes inserting an electro hydrodynamic thrust device into the display case, connecting the electro hydrodynamic thrust device to a power source, and creating an ion wind with the electro hydrodynamic thrust device. The method further includes moving air through the electro hydrodynamic thrust device with the ion wind, ionizing the air in response to reacting the air with the ion wind, and creating reactive oxygen species in response to ionizing the air. The method further includes directing the reactive oxygen species into the display case with the thrust of the ion wind, sanitizing at least one surface in the display case with reactive oxygen species, and reacting ethylene with the reactive oxygen species to break down the ethylene in the display case, thereby reducing the quantity of ethylene in the display case.
[0004] Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a schematic side view of a display case for supporting perishable products according to some aspects of the present invention.
[0006] FIG. 2 is an end view of an electro hydrodynamic thruster according to some embodiments of the present invention.
[0007] FIG. 3 is a cross-sectional view of the electro hydrodynamic thruster taken alone line 3 - 3 of FIG. 2 .
DETAILED DESCRIPTION
[0008] Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways.
[0009] FIG. 1 illustrates a display assembly 10 including a display case 12 that includes a back wall 14 , a bottom wall 16 , and a cover 18 that are supported on legs 20 . The display case 12 has an internal volume that extends between the back wall 14 , the bottom wall 16 and the cover 18 . The illustrated display case 12 includes two shelves 22 a, 22 b each of which include at least one basket 24 a, 24 b for containing and displaying perishable goods, such as flowers. In another embodiment, the baskets 24 a, 24 b are omitted and produce (such as fruits and vegetables) are displayed on the shelves 22 a, 22 b. The cover 18 (typically made of clear glass) is moveable with respect to at least one of the back wall 14 and the bottom wall 16 to permit a user to access the perishable goods. In other constructions, no glass cover is used and the case has an open front and top to provide uninhibited access to the products within the case. Some cases have an open front and are closed on the top and at least some of the sides, whereas other cases have an open top and are closed some or all of the sides. In further constructions, the front and sides of the case are open and the top and back are closed. In still other constructions, the front, sides and top are open and only the back is closed.
[0010] Perishable goods often emit gasses as they are flowering (in the case of flowers) or ripening (in the case of produce). One such gas that is often produced is Ethylene. These gasses often speed up the flowering or the ripening and thus, shorten the shelf-life of the perishable goods. Further, produce often has some bacteria growing on at least one of its surfaces. The bacteria will multiply on the produce as well as on the shelves 22 a, 22 b, even in a refrigerated atmosphere, and especially in the non-refrigerated embodiment shown in FIG. 1 . The bacteria often shorten the shelf-life of the perishable goods.
[0011] The display assembly 10 further includes at least one electro hydrodynamic (EHD) thruster 30 . One such EHD device is described in U.S. Pat. No. 2,765,975 (hereinafter “U.S. Pat. No. 2,765,975”). This EHD device utilizes small wires spaced along a chamber. The small wires are connected to a positive voltage source which ionizes the molecules in close proximity to the charged wires. The voltage in the small wires and the ionized molecules create an ion wind which moves air through the chamber. In contrast to fans and other air-moving devices, the generated ion wind moves the air through the chamber without creating much if any noise.
[0012] One major difference between the present invention and the EDH of U.S. Pat. No. 2,765,975 is that the EHD of U.S. Pat. No. 2,765,975 includes a duct element 30 with ion neutralizing grids 34 that neutralize air prior to exiting the outlet orifice 32 (see col. 2, lines 57-69, FIG. 1 ). However, the present invention would omit such neutralizing elements because the ions are utilized to generate reactive oxygen species (ROS) such as atomic oxygen (O), ozone (O 3 ), hydroxyl (OH), and reactive nitrogen species (RNS) such as nitric oxide (NO), nitrogen dioxide (NO 2 ), etc. The ROS and RNS are created in quantities suitable to kill microorganisms on the perishable goods and within the display case 10 and to neutralize the ethylene produced by the perishable goods. If the ROS and RNS are created in greater quantities, the ROS and RNS may start to react with the perishable goods and thus, shorten the life of the perishable goods. Alternatively, if the ROS or RNS are created in lesser quantities, the microorganisms would multiply substantially unchecked and the ethylene would be allowed to accumulate, thus shortening the life of the perishable goods.
[0013] Another major difference between the present invention and the EDH of U.S. Pat. No. 2,765,975 is that the EHD of U.S. Pat. No. 2,765,975 moves neutralized air at a substantial velocity and is used in place of a fan. In contrast, the present invention moves air with ROS and RNS at a relatively slow velocity to permit the ROS and RNS to have elongated contact with the perishable goods. If the air moves too quickly, the ROS and RNS do not have time to react with the ethylene and kill the microorganisms on the perishable goods and in the display case 10 .
[0014] As shown in FIG. 1 , the EHD 30 moves air as described above and directs the air along an air flow path designated by arrows 36 . The air flow path defines an air curtain over the products within the display area. The air is discharged into the display space from the top through a discharge outlet and the air exits the display space at the bottom from of the case through a return inlet. From the return inlet, the air is recirculated through the EHD 30 . Alternatively, the air can flow in the opposite direction around the display case 10 . A plurality of EHD 30 units can be positioned along the bottom of the display case 10 or an elongate EHD 30 unit can extend along substantially an entire width of the display case 10 .
[0015] An alternative construction for an EHD thruster 130 is shown in FIGS. 2 and 3 . The EHD thruster 130 includes a first insulating tube 132 , an ion collector 134 , a second insulating tube 136 , a corona wire 138 , and an inner tube 140 . An air space 142 is defined between the second insulating tube 136 and the corona wire 138 . Air flows in an air inlet 144 and out an air outlet 146 . A plurality of spacers 148 are placed in the EHD thruster 130 between the second insulating tube 136 and the corona wire 138 to maintain the desired air space 142 . At least one of the corona wire 138 and inner tube 140 can have a spiral design, and thus are easily adapted to different length EHD thrusters 130 because of the spiral design. The corona wire 138 and inner tube 140 can easily be removed from the outer insulating tube 132 for cleaning or replacement.
[0016] A power source 150 , such as an electrical outlet or a battery, is connected to the EHD thruster 130 near the air inlet 144 and is connected to at least one of the ion collector 134 and the corona wire 138 to power the EHD thruster 130 .
[0017] In operation, the EHD thruster 130 can be inserted into a display case, such as the display case 10 of FIG. 1 and can be powered by an electrical outlet or a battery to create a charge near the air inlet 144 and thereby move air through the EHD thruster 130 without requiring the use of any moving parts (e.g., a fan or blower).
[0018] The EHD thruster 30 , 130 produces ROS and RNS and moves the ROS and RNS along a flow path in the display case by means of an ion wind. The ROS and RNS react with at least some of the ethylene and kill at least some of the microorganisms on the perishable goods and in the display case. The EHD thruster lengthens the shelf life of the perishable goods without or without the use of refrigeration.
[0019] In embodiments that utilize an evaporator coil of a refrigeration unit, one or more fans of the refrigeration unit can passively or actively move air through the EHD thruster. For example, the one or more fans can directly move air though the EHD thruster, or can create a small vacuum to draw air into or out of the EHD thruster. In other embodiments, the refrigeration unit can omit any fan or blower and can rely on the ion wind created by the EHD thruster to move air through the evaporator coil.
[0020] Various features and advantages of the invention are set forth in the following claims.
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A display assembly for containing and displaying perishable products includes a case having at least one wall and defining an internal volume, a quantity of gas contained in the case, the gas including ethylene emitted from the perishable products, and an electro hydrodynamic thrust device positioned in the case. The electro hydrodynamic thrust device ionizes a portion of the quantity of gas. The ionized gas includes at least one reactive oxygen species, and the at least one reactive oxygen species reacts with the ethylene to break down the ethylene.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 13/285,524, filed Oct. 31, 2011, now U.S. Pat. No. 9,238,918. This application is incorporated herein by reference in its entirety.
BACKGROUND
[0002] The invention relates to a system (such as a pool system) controlled in part by a motor (such as a motor-powered pump controlling the pool system).
[0003] Pool systems (e.g., swimming pools, hot tubs, spas, whirlpools, jetted tubs, clothes washing machines, and similar apparatuses) typically have auxiliary loads connected to the system that perform different tasks. These task range from heating the fluid within the pool system to sanitizing the fluid within the pool system. These auxiliary loads often require a minimum flow rate of the fluid flowing though them. If the minimum flow rate is not met and the auxiliary load is still operating, then the auxiliary load will not function properly or can be damaged. Therefore, many pump systems for pool systems continually pump the fluid at a rate high enough to meet the minimum flow rate of the auxiliary load connected to the pool system or have sensors within each auxiliary load of the pool system to deactivate the auxiliary load if the minimum flow rate is not met.
SUMMARY
[0004] It has been determined that continually having the flow of fluid at a rate high enough to prevent auxiliary load damage or incorrect functionality wastes energy. Further, having sensors within each auxiliary load is costly for the auxiliary load manufacturers.
[0005] In one embodiment, the invention provides a pool system for controlling an auxiliary load. The pool system includes a vessel to hold a fluid, an auxiliary load, and a pump system coupled to the vessel and the auxiliary load. The pump system pumps the fluid through the auxiliary load. The pump system includes a motor, and a fluid pump powered by the motor, and a controller. The controller controls a pump speed of the pump system, and a power source to the auxiliary load.
[0006] In another embodiment the invention provides a control system for controlling a liquid movement system. The control system includes a controller electrically connected to a motor. The controller controls the speed of the motor. The controller is further electrically connected to an auxiliary load. The controller controls the activation of the auxiliary load based on an inputted maximum time that the auxiliary load is to be activated, and an inputted minimum speed of the motor that the auxiliary load is to be activated at.
[0007] In yet another embodiment, the invention provides a method of controlling a liquid movement system. The method includes receiving a maximum time requirement that an auxiliary load is to operate, receiving a minimum pump speed requirement of a pump system that pumps a liquid through the auxiliary load, monitoring the time that an auxiliary load has been in operation, monitoring the pump speed of a pump system that pumps a liquid through the auxiliary load, and deactivating the auxiliary load if the maximum time requirement or minimum pump speed requirement has been met.
[0008] Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a schematic diagram of a pool system.
[0010] FIG. 1 a is a schematic diagram of another construction of a pool system.
[0011] FIG. 2 is a schematic diagram of a user interface of a controller of the pool system shown in FIG. 1 .
[0012] FIG. 3 is a schematic diagram of the controller of the pool system shown in FIG. 1 .
[0013] FIG. 4 is a perspective view of the motor, controller, and user interface of the controller of the pool system shown in FIG. 1 .
[0014] FIG. 5 is a flowchart implementing a method of controlling a pool system with an integrated auxiliary load control.
DETAILED DESCRIPTION
[0015] Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other constructions and of being practiced or of being carried out in various ways.
[0016] A pool system 100 embodying the invention is schematically shown in FIG. 1 . The pool system 100 generally includes a vessel 105 , an auxiliary load 110 , a pump system 115 , and a controller 120 . The pump system 115 generally includes a motor 116 , a fluid pump 117 coupled to the motor 116 , and a fluid agitator 118 located within the fluid pump 117 .
[0017] In the preferred construction, the vessel 105 is a hollow container such as a tub, pool, or vat that holds a fluid. The fluid can be any type of fluid. In one construction the fluid is chlorinated water.
[0018] As shown in FIG. 1 , the auxiliary load 110 is connected in line with the vessel 105 and pump system 115 by a piping system 125 . The auxiliary load 110 can be a type of pool equipment that receives the fluid originating from the vessel 105 in response to the pump system 115 moving the fluid. In one construction, the auxiliary load 110 is a pool heater used to heat the fluid contained within the vessel 105 and pumped by the pump system 115 through the pool heater. In another construction, the auxiliary load 110 is a saltwater chlorinator used to sanitize the fluid contained within the vessel 105 and pumped by the pump system 115 through the saltwater chlorinator. In another construction, the auxiliary load 110 is a booster pump used to operate a cleaning device within the vessel 105 and pumped by the pump system 115 through the booster pump. In another construction, the auxiliary load 110 is a pool cleaner which is used to clean the bottom of the vessel 105 , and has the fluid from the vessel 105 pumped through the pool cleaner by the pump system 115 . In another construction, the auxiliary load 110 is a solar heater which is used to heat the fluid contained within the vessel 105 and pump by the pump system 115 through the solar heater. In another construction, the auxiliary load 110 is a set of lights and does not receive fluid originating from the vessel 105 .
[0019] FIG. 1 a shows another construction of the pool system 100 . In FIG. 1 a, the auxiliary load 110 connected to the vessel 105 and the pump system 115 with a T-shaped piping system 125 ′, rather than connected in line with the vessel 105 and the pump system 125 .
[0020] As shown in FIG. 1 , the pump system 115 is connected in line with the vessel 105 and the auxiliary load 110 by the piping system 125 . The pump system 115 is used to pump the fluid contained within the vessel 105 through the auxiliary load 110 . The pump system 115 contains a motor 116 , a fluid pump 117 , and a fluid agitator 118 . As is known, the motor 116 takes electrical energy and converts the electrical energy into mechanical energy. The motor 116 can be, for example, a direct-current motor or an alternating-current motor. The motor 116 can also be a single-speed motor, a multi-speed motor, or a variable-speed motor. In one exemplary construction, the motor 116 is a permanent magnet, brushless direct-current (BLDC) motor. As is commonly known, BLDC motors include a stator, a permanent magnet rotor, and an electronic commutator. The electronic commutator typically includes, among other things, a programmable device (a microcontroller, a digital signal processor, or a similar controller) having a processor and memory. The programmable device of the BLDC motor uses software stored in the memory to control the electronic commutator. The electronic commutator then provides the appropriate electrical energy to the stator in order to rotate the permanent magnet rotor at a desired speed.
[0021] The motor 116 is coupled to the fluid pump 117 by a shaft 130 . The fluid pump 117 contains a fluid agitator 118 . In one construction, the fluid agitator 118 is an impeller that controllably moves the fluid contained by the vessel 105 through the auxiliary load 115 . Other pump systems having other fluid agitators may be used without departing from the spirit of the invention.
[0022] As shown in FIG. 1 , the controller 120 is electrically coupled to the auxiliary load 110 and the motor 116 of the pump system 115 . The controller 120 controls the pump speed of the pump system 115 and the activation or deactivation of the auxiliary load 110 . The controller 120 controls the auxiliary load 110 and the pump system 115 based on user inputs. In one construction, the controller 120 is the same controller already contained within the motor 116 , therefore having one controller that both directly controls the speed of the motor 116 and the activation of the auxiliary load 110 . In another construction, the controller 120 is a separate controller from the controller contained within the motor 116 and controls the auxiliary load 110 while controlling the controller contained within the motor 116 , therefore having two separate controllers. An exemplary controller 120 and motor 116 combination is described in U.S. patent application Ser. No. 13/285,624, Attorney Docket No. 028460-8456 US00, filed on even date herewith, the entire content of which is incorporated herein by reference.
[0023] One user input that the controller 120 uses to determine activation or deactivation of the auxiliary load 110 is a user-inputted minimum pump speed of the pump system 115 that the auxiliary 110 can be active at. Different auxiliary loads have different minimum flow rates for the fluid that flows through them. If the flow rate falls below the minimum while the auxiliary load 110 is activated, then the auxiliary load 110 can be damaged or not function properly. The flow rate through the auxiliary load 110 is related to the pump speed of the pump system 115 . Therefore, to prevent damage to the auxiliary load 110 , a user inputs a minimum pump speed of the pump system 115 . Once the pump speed of the pump system 115 falls below the user-inputted minimum pump speed, the controller 120 automatically deactivates the auxiliary load 110 , preventing any possible damage that may be done to the auxiliary load 110 .
[0024] Another user input that the controller 120 uses to determine activation or deactivation of the auxiliary load 110 is a user-inputted maximum time that the auxiliary load 110 is to be activated. Once the user-inputted maximum time is met, the controller 120 deactivates the auxiliary load 110 . In one construction, the user-inputted maximum time is based on a twenty-four hour period. Thus, if for example, a user inputs two hours as the maximum time for the auxiliary load 110 to be activated, the auxiliary load 110 runs for a maximum of two hours every twenty-four hours.
[0025] In another construction, the controller 120 uses a user-inputted maximum pump speed of the pump system 115 that the auxiliary load 110 can be active at. Once the pump speed of the pump system 115 is above the user-inputted maximum pump speed, the controller 120 automatically deactivates the auxiliary load 110 .
[0026] In another construction, the controller 120 uses a user-inputted minimum time that the auxiliary load 110 is to be activated. For example, the controller 120 controls the pump system 115 to operate at the minimum pump speed that the auxiliary load 110 can be active at and activates the auxiliary load 110 for at least the user-inputted minimum time. This ensures that no matter how the normal pump schedule is set the auxiliary load 110 will at least be active for the user-inputted minimum time.
[0027] In another construction, the auxiliary load 110 is a load that does not receive fluid originating from the vessel 105 , but is still controlled by the controller 120 . For example, the auxiliary load 110 is a set of lights which are controlled by the controller 110 to be activated for a user-inputted minimum or maximum amount of time.
[0028] The controller 120 further includes a user interface 200 , as illustrated in FIG. 2 . The user interface 200 includes a display screen 205 , push buttons 210 , and a control knob 215 . The display screen 205 , push buttons 210 , and control knob 215 allow the user to input the minimum pump speed, the maximum pump speed, the maximum time, and the minimum time. The user interface 200 can further include an audio output.
[0029] As shown in FIG. 3 , the controller 120 further includes a microcontroller 300 having a processor 305 and memory 310 . The processor 305 of the controller 120 receives an input from the user interface 200 . The processor 305 then executes a software program, stored in the memory 310 , for analyzing the received signal, and generates one or more control signals that control the activation of the auxiliary load 110 and the motor 116 of the pump system 115 . In one construction, the controller 120 includes a relay switch to activate or deactivate the auxiliary load 110 and an internal clock to measure time.
[0030] FIG. 4 shows a perspective view of one construction of the motor 116 , the controller 120 , and the user interface 200 of the controller 120 .
[0031] In one operation and as shown in FIG. 5 , the user first inputs a normal pump speed schedule 400 using the user interface 200 of the controller 120 . In one construction, where the motor 116 of the pump system 115 is a variable-speed motor, the normal pump speed schedule is a schedule of the pump system 115 operating at different pump speeds. In another construction, where the motor 116 of the pump system 115 is a single-speed motor, the normal pump speed schedule is a schedule of when the pump system 115 is activated or deactivated. In some constructions, the normal pump speed schedule is based on a twenty-four hour period.
[0032] The user then inputs a minimum pump speed at act 405 using the user interface 200 of the controller 120 . The user then inputs a maximum time that the auxiliary load 110 is to be activated at act 410 using the user interface 200 of the controller 120 .
[0033] At act 415 , the controller 120 starts the normal pump speed schedule that was inputted by the user at act 400 . While running the normal pump speed schedule, the controller 120 continually checks if the user-inputted minimum pump speed for the auxiliary load 110 and the user-inputted maximum time the auxiliary load 110 is to be activated has been met. When referring to the controller 120 performing an operation, the processor executes one or more instructions of the software to perform the operation. This may result in the process controlling one or more aspects of the controller 120 or the system either directly or indirectly.
[0034] At act 420 , the controller 120 determines the pump speed of the pump system 115 . For example, at act 425 , the controller 120 determines if the calculated pump speed of the pump system 115 is less than or greater than the user-inputted minimum pump speed. If the calculated pump speed of the pump system 115 is greater than the user-inputted minimum pump speed then the operation proceeds to act 430 where the auxiliary load 110 is activated. If the calculated pump speed of the pump system 115 is less than the user-inputted minimum pump speed then the operation proceeds to act 435 where the auxiliary load 110 is deactivated if it is not already.
[0035] If the auxiliary load 110 is activated at act 430 then the operation proceeds to act 440 where the controller 120 determines the time that the auxiliary load 110 has been active. At act 445 , the controller 120 determines if the determined time is less than or greater than the user-inputted maximum time the auxiliary load 110 is to be active. If the determined time is less than the user-inputted maximum time, then the operation proceeds to act 450 . If the calculated time is greater than the user-inputted maximum time, then the operation proceeds to act 455 . At act 455 the auxiliary load is deactivated.
[0036] At act 450 the controller 120 determines the total time the pool system 100 has been operating. The operation then proceeds to act 460 . At act 460 , the controller 120 determines if the total time period that the pump system 115 operates has been met. In one construction, the total time period is twenty-four hours. If the total time period of the pump system 115 has been met, the operation then proceeds back to act 415 , which restarts the normal pump schedule again. If the total time period of the pump system 115 has not been met then the operation proceeds back to act 420 , where the controller 120 once again checks if the minimum pump speed has been met and if the maximum time has been met, activating or deactivating the auxiliary load 110 as necessary.
[0037] Thus, the invention provides, among other things, a new and useful pool system for controlling an auxiliary load. Various features and advantages of the invention are set forth in the following claims.
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A method of controlling a liquid movement system, such as a pool system. The method includes receiving a maximum time that an auxiliary load is to operate, receiving a minimum pump speed of a pump system that pumps a liquid through the auxiliary load, monitoring the time that an auxiliary load has been in operation, monitoring the pump speed of a pump system that pumps a liquid through the auxiliary load, and deactivating the auxiliary load if the maximum time or minimum pump speed has been met. Also disclosed are a pool system and a controller for controlling the pool system.
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BACKGROUND OF THE INVENTION
The present invention relates to the manufacture of foam sheet stock used in a wide variety of applications, such as for example containers, meat trays, packaging materials and antifriction place mats for airlines food service.
During the manufacture of foam sheet stock from materials such as polystyrene, polyethylene and the like, it is well known to introduce the basic polymer or copolymers into one or more extrusion devices in order to heat the polymer and incorporate therein certain nucleating agents, as well as the blowing agent. The thoroughly heated and masticated plastic material is then extruded through an extrusion orifice into a thin sheet or preferably a tube. When the extrudate takes the shape of a tube, it is drawn over a mandrel, thus expanding the circumferential extent of the tube. In addition, the tube of foam material is pulled away from the mandrel at a speed greater than the extrusion speed, thus inducing a certain amount of orientation into the foam sheet material. The orientation in a cellular foam sheet is a desirable feature in that certain memory characteristics can be built into the foam sheet. For example, it is now common to sever rectangular shaped pieces of foam sheet material and form them into cylinders having an overlapped liquid impervious seam. The cylinder thus formed is placed on a mandrel and subjected to controlled heat, thus causing the foam material to shrink and assume the configuration of the mandrel. Both one and two-piece drinking cups have been manufactured in this manner. Then too, a protective cover for bottles has been used for several years in the carbonated beverage field.
In order to monitor newly created foam sheet material, it is highly desirable to be able to examine in minute detail the actual cell structure within the sheet. Microscopic examination at, for instance, 60X magnification reveals several important aspects of how well the foam sheet has been fabricated. For example, it is highly important that the individual cells be of closed configuration if the ultimate purpose of the sheet material is for the fabrication of containers such as coffee cups and the like. A close-up examination of the cells within the sheet material reveals how well the surfaces of the foam material have been cooled. If the cooling is too rapid, small cell sizes will be created, thus acting as a bar to adequate cooling of the cells situated in the center of the sheet. Cells that receive inadequate cooling will have a tendency to rupture, thus reducing the overall integrity and usefulness of the sheet material. A good microscopic examination will reveal whether there has been an overload of the blowing agent and in the instance of a laminate, the skin thickness and uniformity can be monitored. A microscopic examination also permits an insight into the physical dimensions of each cell within the foam structure and its relationship with adjacent cells. As a foam material is generated soon after extrusion, the cells are normally spherical in configuration. With the introduction of orientation into the foam material, the originally spherical cells assume an elongate shape which they retain until subsequently released by the application of heat. Thus it becomes evident for several reasons to rely upon good microscopic examination of the individual cell structure in foam sheet material to assure adequate quality control.
SUMMARY OF THE INVENTION
The present invention relates to an apparatus for the preparation of foam sheet samples for microscopic examination. More particularly, the invention relates to an apparatus that permits a precisely measured laboratory foam sheet cross-sectional specimen to be prepared.
Foam sheet stock suitable for the manufacture of containers such as coffee and soft drink cups has an overall thickness in the range of 0.015 inch to 0.040 inch and a density of 10-15 pounds per cubic foot. Consequently, it is difficult to sever a thin parallel sided strip of foam sheet so that its edge structure can be examined microscopically. To cut such samples by the use of tools, such as scissors, would crush the delicate cell structure to such an extent that a detailed examination of the exposed sheet edge would not be meaningful. Thus it becomes imperative that the foam sheet samples be severed by means of a thin cutting blade such as a razor blade.
With this in mind it is one of the objects of the present invention to provide an apparatus that will grasp a foam sheet sample and permit a series of very linearly oriented parallel cuts to be made thereon.
The present apparatus includes a base structure for stabilization of the device and a clamping arrangement to grasp the foam sheet specimen without damaging it to the extent samples cannot be severed therefrom. The foam sheet can be advanced through the apparatus a prescribed amount and a planar surface is provided for the interaction with a cutting knife. Since the apparatus employs a screw thread specimen advance mechanism, it is possible to prepare repetitive samples, each having a uniform thickness with very parallel cut edges exposed for microscopic examination.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the sample preparation apparatus of the present invention.
FIG. 2 is a fragmentary sectional view, taken along lines 2--2 of FIG. 1 which shows the bottom tie-down connection for the hand nut.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The apparatus of the present invention is shown in FIG. 1. The overall apparatus is represented by numeral 10. The apparatus 10 represents a compact device for manipulating a foam sheet sample such as that depicted at 12. The foam sample 12 is prepared for use with apparatus 10 by first cutting it to a rectangular configuration.
In particular, apparatus 10 is supported by a base plate 14. Base plate 14 is generally rectangular in shape and is preferably constructed of metal. Two upright support columns 16 and 18 are attached to the top planar surface of base plate 14. The tops of support columns 16 and 18 are tied together by means of top deck plate 20. A support bar 22 is attached to the top surface of top deck plate 20 and is cantilevered so that it extends in a horizontal direction over the base plate 14. A clamp bar 24 is positioned adjacent one side of support bar 22 and is held in aligned engagement with support bar 22 by means of the threaded studs 26 and 28 which are anchored in support bar 22. Wing nuts 30 and 32 which coact with studs 26 and 28 provide a means for moving clamp bar 24 against support bar 22. The manner of use and function of the clamp bar 24 positioning and its use will be explained in more fully infra.
Returning once again to base plate 14, vertically aligned posts 34 and 36 are oriented to one another in spaced apart parallel positioning which is also perpendicular to base plate 14. Posts 34 and 36 are attached to the top of base plate 14 by conventional means (not shown). The top section 38 of posts 34 and 36 are of reduced diameter and coact with the bifurcated ends of saddle bar 40. Thus, as shown in FIG. 1, the saddle bar 40 is restrained from rotation by the engagement provided by posts 34 and 36. However, saddle bar 40 has freedom of movement in a vertical direction. Saddle bar 40 is rigidly attached, by a fastener such as bolt 42, to the top surface of threaded member 44. Threaded member 44 is of cylindrical configuration and is threaded with a low pitch thread on its exterior. An internally threaded hand nut 46 contains a centrally positioned internal bore that is threaded to match the threads on threaded member 44. Hand nut 46 is adapted for rotation both clockwise and counterclockwise and is rotatably anchored to base plate 14.
FIG. 2 which is a fragmentary cross-sectional view, further shows how hand nut 46 is attached to the top of base plate 14. An aperture 48 is placed in the bottom center of hand nut 46. A pivot pin 50 is passed through aperture 48, as well as a similar diameter aperture in bushing 52. Bushing 52 is pressed into an accommodating hole in base plate 14. The bushing 52 contains a flange 54 that provides sufficient space between the bottom of hand nut 46 and the top of base plate 14 so that there is no interference as hand nut 46 is rotated. The lower end of pivot pin 50 is grooved for the reception of a retaining ring 56 as shown in FIG. 2. Since hand nut 46 is held captive by means of pivot pin 50, its movement in the vertical direction is zero. However, when hand nut 46 is rotated, threaded member 44 will move in an upward or downward direction depending upon which direction hand nut 46 is rotated. Hand nut 46 has a large diameter flange-like disc 58 incorporated as an integral part of its lower extremity. Disc 58 is of sufficient overall diameter and thickness that it can be easily manipulated by hand. To further aid in the rotation of disc 58, notches 60 are positioned in a circumferentially spaced array around the periphery of disc 58. Interdispersed between notches 60 are bushings 62 which are carefully laid out so that the circumferential spacing therebetween is in equal increments. Each bushing 62 is in radial alignment with respect to the axis of rotation of hand nut 46. A detent mechanism 64 is positioned outboard of hand nut 46 and in radial alignment with the rotational axis of hand nut 46. The leading edge of detent mechanism 64 is adapted to enter bushings 62, thus securing hand nut 46 from rotation so long as the detent is engaged. The detent mechanism 64 is spring biased (not shown) and is operated by applying a radially outward force to the handle. The detent mechanism 64 is held in position by post 66 which is fastened to base plate 14.
Directing our attention once again to saddle bar 40, which is affixed to the top of threaded member 44, a lower clamp mechanism 68 is mounted on the top of saddle bar 40. The lower clamp mechanism 68 is positioned beneath the upper support bar 22. A clamp block 70 is attached to saddle bar 40 and its inboard face is in vertical alignment with the inboard face of support bar 22. A movable clamp pad 72 is positioned so that it will coact with clamp block 70. The clamp block 70 is attached to the end of screw 74. The attachment of screw 74 to clamp block 70 permits screw 74 to rotate without clamp block 70 also rotating. Screw 70 is held in position and in threaded engagement with support post 68. A convenient handle 78 is attached to screw 74 to facilitate the movement of clamp pad 72 into and out of clamping engagement with clamp block 70.
During the operation of overall apparatus 10, a foam sample, such as that depicted at 12, is sheared to a rectangular size that will permit it to be inserted in the expanse between studs 26 and 28 of support bar 22. The foam sample 12 is accommodated in the space between support bar 22 and clamp bar 24 and is lowered until its bottom edge rests firmly against the top surface of saddle bar 40. The foam sample 12 also passes between the gripping surfaces of clamp block 70 and coacting clamp pad 72. After the foam sample 12 has been positioned as described abovee, the lower clamp pad is moved into firm engagement with foam sample 12, thus clamping it into an immobile position with respect to saddle bar 40. The top clamp bar 24 is moved into engagement with foam sample 12, however, care is taken to only exert enough force to remove the slight curl which is inherent in foam sheet stock samples. This force is achieved by slowly tightening wing nuts 30 and 32 so that clamp bar 24 maintains its parallel orientation with respect to support bar 22. Thus when clamp bar 24 is in final position, it will have removed the curvature or curl from foam sample 12, yet it will not impede the free movement of foam sample in the vertical direction. At this point in the test procedure and sample preparation, it is desirable to permit an excess of foam sheet 12 to protrude above the top surfaces of support bar 22 and clamp bar 24. The hand nut 46 can, for example, be placed at stop position number 1 by removing detent mechanism 64 and reinserting it in the bushing 62 corresponding to position number 1 when the overall apparatus 10 and its included foam sample are in a position thus described above. A sharp instrument, such as a razor blade, is used to cut and remove that portion of foam sample 12 that protrudes above the surfaces of support bar 22 and coacting clamp bar 24. To assure an even cut across the expanse of foam sample 12, the cutting edge of the razor blade is held against the surfaces of support bar 22 and clamp bar 24. The just mentioned surfaces are at the same elevation, thus assuring that the newly cut surface of foam sample 12 is perpendicular to its planar side surfaces.
The hand nut 46 is freed from its locked position by retracting detent mechanism 64. Hand nut 46 is repositioned at stop position number 2. The slight turn of hand nut 46 from stop position 1 to stop position 2 results in the raising of foam sample 12 by 0.004 inch. This specific increment in the raising of the top edge of foam sample 12 above the top surfaces of support bar 22 and clamp bar 24 is achieved because of the following arrangement. The 0.004 inch rise of saddle bar 40 and its attached foam sample 12 is attributable to the laying out of the center lines of bushings 62 at angles of 25.714 degrees which results from 360 degrees divided by 14 equal stop positions. The thread employed on threaded member 44 is an 18 pitch thread, thus one revolution divided by 14×18 equals 0.00396 inch or when rounding off, 0.004 inch.
After hand nut 46 has been advanced to stop position 2, the razor blade is once again utilized to sever a 0.004 inch thick slice of foam material from the top edge of foam sample 12. The 0.004 inch sample is then carefully removed and mounted on double sticky back tape on a microscope slide.
If foam samples of greater thickness are desired, hand nut 46 is advanced more than one stop, thus resulting in sample thicknesses which are multiples of 0.004 inch.
Thus the present invention provides samples for another physical test in addition to other tests such as tensile, stretch, elongation, solvent resistance and surface cell size. The present invention permits test samples to be prepared which is an aid to establish performance criteria, for example, two foam materials may appear equal in physical tests, as well as in residual blowing agents, yet one foam material may be brittle and the other flexible or two different foam materials of the same caliper and density may vary as to their respective insulative qualities. An insight as to the differences between such foam materials can be gained by examining the precisely cut foam samples as prepared by the present invention.
Then too, the method provided by the present invention provides for the severing of foam test samples that have at least two cut sides that are parallel to one another. The present method preserves the structure of the individual cells within the sample so that the cells may be examined without undue distortion or mutilation occurring because of the sample preparation. The precise parallel orientation of the cut surfaces of the foam samples permits even transmission of light through the specimen during its microscopic examination.
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A device for aiding in the preparation of very thin slices of foam sheet material that is to be examined under a microscope. The device has a clamp arrangement for holding a sample of foam sheet material. A screw feed arrangement permits the foam sheet material to be advanced past a planar surface where a very thin slice of foam material can be removed. A clamping arrangement keeps the foam sheet material in linear alignment at the location where the sample is severed. A detent arrangement permits a metered amount of foam sheet material to be advanced past the planar cutting surface by the screw feed arrangement.
The method of preparing a foam sample by first severing the foam material while it is held by the apparatus, thus establishing a planar cut, then positioning the material for a second cut which is then made parallel to the first cut.
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BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates to a method and a machine for making belting with a woven single-layer central portion and two tubular edge portions. Beltings of this type are disclosed in German Patent Publication No. 2,508,732. It is an object of the present invention to manufacture this type of belting at a higher speed and therefore at a lower cost than has heretofore been possible.
A belting with two tubular edge portions such as are used in safety belts in vehicles can be woven in a relatively simple manner on a shuttle ribbon weaving machine. However, such machines do not allow high production speeds due to the high mass of the shuttle and the machine elements employed to move the shuttle. Also, the shed formed on such machines is of a relatively large size and a large reed motion is necessary for the shuttle. In addition, much time is consumed for spooling the weft thread for the shuttle.
Utilization of a gripper ribbon weaving machine only slightly increases the production speed for such belts. Although the gripper has a smaller mass than the shuttle, the gripper has a considerable length in relation to the width of the woven belting so as to provide space for the passage of the tuck bobbin. This again results in the formation of a large shed and a large reed motion.
Besides the mass of the gripper, the tuck bobbin must also be moved so that, together, considerable increase in the production speed is prevented. Again, in this type of machine, the tuck thread has to be spooled.
The production speed can be raised considerably by means of the fabric structure of the present invention. According to the present invention, a needle ribbon weaving machine which is known, per se, in this art is utilized where a weft insert needle which is shorter and thinner than the gripper of the gripper machine is employed. Further, this type of machine has a knitting needle with a latch which can be readily employed to fix the weft thread loops formed by the weft inserting needle along one of the belting edges by means of a tuck thread. The tuck thread in such arrangements need not be spooled but can be fed off from a cone or cop.
For making one of the tubular edge portions there is first woven a single-layer fabric which is then closed to form the tubular edge portion in the working sequence immediately after every second double pick of the inserting needle by means of the pull of the associated weft thread. According to the present invention, one of the tubular edge portions is formed in a known manner while the opposite tubular edge portion is manufactured according to the present invention and is located on the side of the belt reached by the inserting needle moving from the first edge portion across the shed to the opposite edge of the belt.
In such structures, a knitting course must be provided at one of the belting edges. However, such knitting courses become worn during the life of the belting and if the belting is used as a safety-belt in vehicles, the edges of the belting rub against the clothes of a person wearing the belt as well as against the shackles of automatic seat belt mounting devices. If the knitting course is destroyed by such wear, the anchoring of the weft thread loops by the tuck thread is lost and the belting would be destroyed. It is especially dangerous, when the belt is used as a safety belt, where the destruction occurs at first only partially as such localized wear is unnoticed so that the resulting decrease in strength of a belt will not be detected.
Generally is also undesirable to have a thick and therefore projecting knitting course since it results in the formation of belting edges which are very rough and can result in discomfort to a wearer.
It is insufficient merely to displace the knitting course from the medium plane of the belting to the upper or lower attaching line or joint of the second tubular edge portion since the knitting course itself would then be subject to much wear and would abrade against the clothing of the person wearing the belt. provide
It is therefore an important object of the present invention that the foregoing disadvantages be obviated and a strong yet comfortable belting structure be provided. To this end, the tuck thread loops are drawn by the weft loops a certain distance into the central portion of the belt fabric. For example, the tuck thread loops may be drawn a distance of approximately 5 mm within the central portion so that, in effect, for this narrow strip, the weft threads are replaced by tuck threads. This will not change the character of the fabric in the central portion of the belt in any practical sense and will not be noticed. The knitting course will therefore no longer be occupied with the tops or ends of the weft loops and the two ends of the tuck thread loops which are interlocked with an associated end of a weft loop as these sections of the threads are displaced into the single-layer central portion of the fabric. As a result, the thickness of the knitting course is considerably reduced and will not project beyond the normal thickness of the fabric. Also, a soft tubular edge portion will be obtained and the knitting course will not be subjected to any greater wear than the other portions of the belting.
In an alternative embodiment, where it is desired to prevent laddering in the fabric which can destroy the belt, the present invention employs an additional thread, termed a locking thread, which is worked into the knitting course by means of the knitting needle. Following the method of the present invention, even though the use of an interlocking thread renders the knitting course thicker, the knitting course can still be worked into the fabric to a sufficient depth so that it will not noticeably project.
By a further modification, according to the present invention, a normal needle ribbon weaving machine is made suitable for carrying out the method of the present invention by inserting a transmission in the tuck thread feeding device.
Since the single-layer central portion of the belt and the second tubular edge portion have twice the number of tuck threads per meter as compared with the number of weft threads, the tuck thread should be twice as fine as the weft thread. The choice of the weft threads according to the desired characteristics of the belting is therefore limited. In accordance with a further embodiment of the present invention, a belting can be produced without the use of a tuck thread but which retains the above-stated advantageous properties of the belt. According to this embodiment, a pick is always knitted with the preceding pick and with an interlocking thread in making the knitting course. Surprisingly, the knitting course can be inserted easily and with sufficient depth into the belting if the interlocking thread is laid into the head of the knitting needle from a point vertically above, that is, in a downward direction relative to the belt as related to the normal arrangement of a ribbon weaving machine. The single layer ribbon portion which is first made is folded around to the upside and is then drawn onto the central portion. The upper or topside of the belting is therefore that side on which the single layer ribbon portion for making the tubular edge portion is fixed to the central portion of the belting by means of the knitting course.
Conventional needle ribbon weaving machines do not allow the interlocking thread to be guided above the knitting needle and do not allow the feeding of the interlocking thread from vertically above to the head of the knitting needle. According to the present invention, the needle ribbon weaving machine is improved and made suitable for this type of feeding. In particular, during the necessary rocking motion of the knitting needle with its needle holder, an elastic thread-guide is bent in such a way that the interlocking thread guided by the longitudinal eye is laid into the head of the knitting needle in a correct manner from a point vertically above.
The foregoing and other objects of the present invention will become apparent as consideration is given to the following detailed description taken in conjunction with the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a belting structure according to the first embodiment of the present invention;
FIG. 2 is an enlarged sectional view of the right-hand tubular edge portion of the embodiment of FIG. 1;
FIG. 3 is a schematic top plan view of a manufacturing step in the production of the belting of FIGS. 1 and 2;
FIG. 4 is a schematic top plan view of the manufacture of belting according to the second embodiment; and
FIG. 5 is a side view of a needle ribbon weaving machine for laying in the interlocking thread in the arrangement of FIG. 4.
DETAILED DESCRIPTION OF THE INVENTION
The belting according to FIGS. 1 and 2 has a first tubular edge portion 1, a second tubular edge portion 2 and a single-layer central portion 4. In the weaving operation, the weft inserting needle is moved in the direction of the arrow 6 into the shed here not shown and is returned in the opposite direction. The tubular edge portion 1 is made by a double pick operation in a conventional manner.
For making the second tubular edge portion 2 there is made first a single-layer fabric 2', in the present case by utilizing the ground or main warp threads only. As explained below, when the weft insert needle returns, the fabric is closed to form the second tubular edge portion 2. Simultaneously, a knitting course 8 is made at the joint of the upper fabric layer 2.1 of the tubular edge portion 2 and the right-hand edge 4a of the single-layer central portion 4.
FIG. 2 shows schematically the right-hand portion of the belting with the warp threads 10 in the single-layer central portion 4 and the warp threads 12 in the second tubular edge portion 2 in cross-section. As shown, the knitting course 8 is well inserted into the fabric without protruding upwards.
The manufacture of the belting will now be described in detail with reference to FIGS. 2 and 3 showing the second tubular edge portion and the adjacent part of the central portion 4. The fabric of the central portion and of the tubular edge portion are shown in a simplified manner, but it should be understood that the central portion is made in a twill weave and the tubular edge portion in a linen tubular weave.
For making the single-layer central portion, there is provided a group 10 of warp threads of which group only the right-hand portion is shown. For making the second tubular edge portion 2, there are provided warp threads of a group 12 arranged with double density as compared with the warp threads of the group 10. The lower portion of FIG. 3 shows schematically the finished fabric with the second tubular edge portion 2. Only the ground warp threads are utilized for making the second tubular edge so that at first, in the same way as with the central portion 4, a single-layer fabric is produced which later, due to the reed motion of the loom, is drawn around to form the tubular edge portion.
After a shed has been formed, the weft inserting needle 14 is pushed from the left to the uppermost right-hand side through the shed to form a loop 16.1 of the weft thread 16. A tuck thread guide 18 guides the tuck thread 20 through the loop 16.1 of the weft thread and lays the tuck thread into the head of the knitting needle 21 which head is opened at that time. FIG. 3 shows the weft inserting needle 14 while it is returning to the left.
Further an interlocking thread guide 22, which may be attached to the reed, guides the interlocking thread 24 from the knitting course 8 below the knitting needle 21. By an upwards motion of the interlocking thread guide 22, the interlocking thread 24 is laid into the head of the knitting needle 21.
The knitting needle 21 is making stitches 25 out of the weft tuck and interlocking threads and is thus forming the knitting course 8 shown only schematically.
When the inserting needle 14 returns to the left, the weft thread loop 16.1 is drawn to the left and in so doing is taking with it a tuck thread loop which has been made just then from the tuck thread 20. It further draws with it the previous loop 20.2 now knocked-over from the knitting needle 21. By this time two heads 20.4 and 20.6 of tuck thread loops are hanging in the head of the drawn back weft thread loop 16.2 as shown in FIG. 3 for the previous pick. Contrary to the previously known method, there is fed so much tuck thread that, during the reed motion, the two heads 20.4 and 20.6 of the tuck thread loops are drawn by the weft thread loop 16.1 a distance of e.g. 5 mm into the fabric of the single-layer central portion 4. FIG. 2 shows that the tuck thread loop 20.5 extends a short way into the knitting course 8 while the tuck thread loop 20.7 forms the circular edge portion 2 with the warp threads and then also extends into the knitting course 8.
The weft thread loop 16.1 (FIG. 3) is fastened to the outer edge of the first made single-layer fabric 2' (FIG. 1) by means of the tuck thread 20 and the interlocking thread 24. As a consequence, the weft thread draws the single-layer fabric 2' around to form the tubular edge portion 2.
Thus, the knitting course 8 is relieved of the heads of the tuck loops 20.4 and 20.6 and of the heads of the weft thread 16.2. The knitting course, thus unencumbered, disappears in the fabric as shown in FIGS. 1 and 2.
Known needle ribbon weaving machines are feeding the tuck thread at the normal speed which is just sufficient for making a knitting course. Since, according to the invention, much more tuck thread is necessary than in normal cases for making the long tuck thread loops 20.5 and especially 20.7 with every second pick, the tuck thread feeding speed must be increased considerably, e.g. by a factor 4. Therefore a suitable transmission can be built into the tuck thread feeding device. Since a known transmission can be used for this purpose it is not shown in the drawings.
Somewhat less weft thread is needed than in normal cases since the weft thread loops 16.1 are a little shorter than normally. This is achieved by a somewhat smaller feeding speed of the weft thread.
The weft, tuck and interlocking threads are not spooled but run off from cones or cops.
In the embodiment according to FIGS. 4 and 5, the weft thread 16 is also making the second tubular edge portion 2 of which only the upper fabric layer 2,1 is shown. A knitting course 8 is made also in this embodiment at the place shown in FIGS. 1 and 2. The knitting course is made ladderproof by knitting in an interlocking thread 24. The head of the knitting needle 21 is directed to the right upper side and has an inclination of about 45 degrees with respect to a horizontal plane, as shown in FIG. 4.
FIG. 5 shows details of the needle ribbon weaving machine as seen from the right-hand side in FIG. 4. The knitting needle 21 is held fast by a needle holder 30 which itself can be rocked about a horizontal axis 32 at the machine frame 34. The reed 38 can be rocked about a second horizontal axis 36 at the machine frame. Both axes 32 and 36 are parallel to each other. FIG. 5 shows also yarns of the groups 10 and 12 of the warp threads.
An interlocking thread guide 40 is provided for laying-in the interlocking thread 24. This thread guide has an upper horizontal arm 42 whose left end is attached to the needle holder 30 and is rotatable about an axis 44. The thread guide 40 has a lower arm 46 whose left end is fastened to the machine frame 34 by a bolt 47. The thread guide 40 is bent from spring steel wire and has a substantially vertical web 50 and at its right upper corner an upright longitudinal eye 48 for guiding the interlocking thread 24.
In operation, the needle holder 30 makes a rocking movement in the direction of the double headed arrow 52 whereby the knitting needle 21 is moved to and fro for about 15 mm in the direction of the double headed arrow 54. During its to and fro motion the needle holder 30 takes with it the upper arm 42 of the interlocking thread guide 30 while the lower arm 46 of the thread guide is fixed to the machine frame. Therefore the thread guide is bent in such a way that the eye 48 makes an up and down movement in the direction of the double headed arrow 56.
In operation of the machine, the inserting needle 14 (see FIG. 4) is advanced to the right-handed side through the open shed while the knitting needle 21 is moving to the upper side of FIG. 4 which is the right-hand side in FIG. 5. The inserting needle lays the weft thread 16 into the open head of the knitting needle 21. The interlocking thread 24 runs from the knitting course 8 above the knitting needle 21 to the eye 48 of the interlocking thread guide. When the eye 48 is lowered, the interlocking thread guide is laid into the then open head of the knitting needle. FIG. 5 shows a later phase of the operation when the knitting needle 21 is returning again to the left and the previous stitch 60 is about to close the latch of the knitting needle 21 and to be knocked over.
The first made single-layer fabric 2' (FIG. 1) is drawn around to form the second tubular edge portion when the weft thread 16 is drawn back while the inserting needle 14 is returning to the left in FIG. 4.
Laying-in the interlocking thread 24 from above leads to the desired result that the knitting course 8 is drawn deeply into the fabric of the central portion 4 and does not project upwards.
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A belting with a single-layer central portion and two tubular edge portions is made on a needle ribbon weaving machine with one of the tubular edge portions woven as a single layer and then closed to form the tubular edge portion by exerting a pull on the weft thread; a knitting course maintains the tubular edge portion closed along its joint by means of a tuck thread and/or an interlocking thread which is buried in the fabric by feeding a greater length of tuck thread in the knitting course than usual or by laying in the interlocking thread into the head of the knitting needle from vertically above the knitting needle.
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FIELD OF THE INVENTION
[0001] The present patent application relates to the use of compounds derived from trimethylolpropane oxetane as inverters in self-invertible inverse latexes.
BACKGROUND OF THE INVENTION
[0002] Inverse latexes of polyelectrolytes based on partially or completely salified 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid (also known as 2-acrylamido-2-methylpropanesulfonic acid, ATBS or AMPS), and their use in cosmetics and/or in pharmaceuticals have formed the subject matter of numerous patent applications. However, the presence of significant amounts of water and oil in these inverse latexes represents a not insignificant disadvantage in terms of volume, of cost and sometimes of increased risks and/or of toxic effects.
[0003] Solutions have thus been developed for increasing the concentration of polyelectrolytes in the final inverse latexes, for example by subjecting the reaction medium, at the end of polymerization, to a vacuum distillation stage in order to remove a more or less large portion of water and oil. However, this distillation is problematic to carry out as it often brings about a destabilization of the inverse latex which is necessary to counter by the prior addition of stabilizing agents. European patent applications EP 0 161 038 and EP 0 126 528 and British patent application GB 1 482 515 disclose such a use of stabilizing polymers.
[0004] The disadvantage of these stabilizing products is that they comprise alcohols or glycols which can cause environmental problems. Furthermore, sometimes the reaction medium sets solid during the distillation stage, without this phenomenon ever having been truly explained, but the certain consequence of which is the destruction of the batch of inverse latex in the course of preparation and difficult and expensive cleaning of the reactor used. Finally, even if the distillation takes place correctly, the inverse latexes obtained often invert with difficulty when they are employed in an aqueous phase and they also exhibit a high viscosity and sometimes microgels within them. These disadvantages thus prohibit their use in the manufacture of cosmetic formulations and/or of textile printing pastes. In order to overcome these disadvantages, the inventors have developed an inverse latex disclosed in the French patent application published under the number FR 2 879 607 comprising from 50% to 80% by weight of a polyelectrolyte comprising from 0.01 mol % to 10 mol % of at least one monomer unit derived from the compound of formula (A):
[0000] C(R 1 )(R 3 )═C(R 2 )—C(═O)—O—(CH 2 —CH 2 —O) n —R 4 (A)
[0000] in which the R 1 , R 2 and R 3 radicals, which are identical or different, represent, independently of one another, a halogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, the R 4 radical represents a saturated or unsaturated and linear or branched aliphatic radical comprising from 6 to 30 carbon atoms and n represents a number between 1 and 50.
[0005] However, when this composition is used to prepare a thickened formulation, the rate of inversion of the inverse latex in the aqueous phase, that is to say the time necessary to obtain the maximum development of the viscosity, remains fairly low, which means, for the user, a loss of time during the use of this product, in particular in the industrial phase for preparing cosmetic formulations and/or textile printing pastes. This is because it is well known that the inversion time for inverse latexes increases very considerably as a function of the scale of use. Furthermore, the stability over time of the inverse latexes described in FR 2 879 607 is not completely satisfactory. This is because a fairly rapid phenomenon of release of oil at the surface is observed during storage.
[0006] The inventors have thus sought to develop inverse latexes which do not exhibit the abovementioned disadvantages.
SUMMARY OF THE INVENTION
[0007] According to a first aspect, the subject matter of the invention is a surfactant composition (C) which comprises, per 100 mol %:
1)—a proportion of greater than or equal to 10 mol % and of less than or equal to 50 mol % of a composition (C II ) comprising, per 100 mol %:
α)—from 60 mol % to 100 mol % of a compound of formula (II):
[0000]
[0000] in which:
R2 represents a linear or branched alkyl radical comprising 12 carbon atoms, T 1 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m1 —H radical in which m1 is an integer of greater than or equal to zero and less than or equal to ten, T 2 , which is identical to or different from T 1 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m2 —H radical in which m2 is an integer of greater than or equal to zero and less than or equal to ten, and T 3 , which is identical to or different from T 1 and T 2 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m3 —H radical in which m3 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m1+m2+m3 is greater than 0 and less than or equal to ten;
β)—optionally up to 40 mol % of a compound of formula (II′):
[0000]
[0000] in which:
R′ 2 represents a linear or branched alkyl radical comprising 14 carbon atoms, T′ 1 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m1 —H radical in which m1 is an integer of greater than or equal to zero and less than or equal to ten, T′ 2 , which is identical to or different from T′ 1 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m2 —H radical in which m2 is an integer of greater than or equal to zero and less than or equal to ten, and T′ 3 , which is identical to or different from T′ 1 and T′ 2 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m3 —H radical in which m3 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m1+m2+m3 is greater than 0 and less than or equal to ten; and
γ)—optionally up to 10 mol % of a compound of formula (II″):
[0000]
[0000] in which:
[0022] R″ 2 represents a linear or branched alkyl radical comprising 16 carbon atoms,
T″ 1 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m1 —H radical in which m1 is an integer of greater than or equal to zero and less than or equal to ten, T″ 2 , which is identical to or different from T″ 1 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m2 —H radical in which m2 is an integer of greater than or equal to zero and less than or equal to ten, and T″ 3 , which is identical to or different from T″ 1 and T″ 2 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m3 —H radical in which m3 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m1+m2+m3 is greater than 0 and less than or equal to ten; 2)—a proportion of greater than or equal to 50 mol % and of less than or equal to 90 mol % of a composition (C III ) comprising, per 100 mol %:
α)—from 60 mol % to 100 mol % of a compound of formula (III):
[0000]
[0000] or of its isomer of formula (IV):
[0000]
[0000] or of the mixture of these two isomers,
in which formulae (III) and (IV):
R2 represents a linear or branched alkyl radical comprising 12 carbon atoms, T 4 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m4 —H radical in which m4 is an integer of greater than or equal to zero and less than or equal to ten, T 5 , which is identical to or different from T 4 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m5 —H radical in which m5 is an integer of greater than or equal to zero and less than or equal to ten, T 6 , which is identical to or different from T 4 and T 5 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m6 —H radical in which m6 is an integer of greater than or equal to zero and less than or equal to ten, T 7 , which is identical to or different from T 4 , T 5 and T 6 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m7 —H radical in which m7 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m4+m5+m6+m7 is greater than 0 and less than or equal to ten;
β)—optionally up to 40 mol % of a compound of formula (III′):
[0000]
[0000] or of its isomer of formula (IV′):
[0000]
[0000] or of the mixture of these two isomers,
in which formulae (III′) and (IV′):
R′ 2 represents a linear or branched alkyl radical comprising 14 carbon atoms, T′ 4 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m4 —H radical in which m4 is an integer of greater than or equal to zero and less than or equal to ten, T′ 5 , which is identical to or different from T′ 4 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m5 —H radical in which m5 is an integer of greater than or equal to zero and less than or equal to ten, T′ 6 , which is identical to or different from T′ 4 and T′ 5 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m6 —H radical in which m6 is an integer of greater than or equal to zero and less than or equal to ten, and T′ 7 , which is identical to or different from T′ 4 , T′ 5 and T′ 6 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m7 —H radical in which m7 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m4+m5+m6+m7 is greater than 0 and less than or equal to ten; and
γ)—optionally up to 10 mol % of a compound of formula (III″):
[0000]
[0000] or of its isomer of formula (IV″):
[0000]
[0000] or of the mixture of these two isomers,
in which formulae (III″) and (IV″):
R″ 2 represents a linear or branched alkyl radical comprising 16 carbon atoms, T″ 4 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m4 —H radical in which m4 is an integer of greater than or equal to zero and less than or equal to ten, T″ 5 , which is identical to or different from T″ 4 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m5 —H radical in which m5 is an integer of greater than or equal to zero and less than or equal to ten, T″ 6 , which is identical to or different from T″ 4 and T″ 5 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m6 —H radical in which m6 is an integer of greater than or equal to zero and less than or equal to ten, and T″ 7 , which is identical to or different from T″ 4 , T″ 5 and T″ 6 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m7 —H radical in which m7 is an integer of greater than or equal to zero and less than or equal to ten, it being understood that the sum m4+m5+m6+m7 is greater than 0 and less than or equal to ten.
[0049] According to another specific aspect of the present invention, said surfactant composition (C) as defined above additionally comprises:
3)—up to 5 mol % of a composition (C V ) comprising, per 100 mol %:
α)—from 60 mol % to 100 mol % of a compound of formula (V):
[0000]
[0000] in which:
R2 represents a linear or branched alkyl radical comprising 12 carbon atoms, T 8 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m8 —H radical in which m8 is an integer of greater than or equal to zero and less than or equal to ten, T 9 , which is identical to or different from T 8 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m9 —H radical in which m9 is an integer of greater than or equal to zero and less than or equal to ten, and it being understood that the sum m8+m9 is greater than 0 and less than or equal to ten;
β)—optionally up to 40 mol % of a compound of formula (V′):
[0000]
[0000] in which:
R′ 2 represents a linear or branched alkyl radical comprising 14 carbon atoms, T′ 8 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m8 —H radical in which m8 is an integer of greater than or equal to zero and less than or equal to ten, T′ 9 , which is identical to or different from T′ 8 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m9 —H radical in which m9 is an integer of greater than or equal to zero and less than or equal to ten, and it being understood that the sum m8+m9 is greater than 0 and less than or equal to ten; and
γ)—optionally up to 10 mol % of a compound of formula (V″):
[0000]
[0000] in which:
R″ 2 represents a linear or branched alkyl radical comprising 16 carbon atoms, T″ 8 represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m8 —H radical in which m8 is an integer of greater than or equal to zero and less than or equal to ten, T″ 9 , which is identical to or different from T″ 8 , represents a hydrogen atom or a (—CH 2 —CH 2 —O—) m9 —H radical in which m9 is an integer of greater than or equal to zero and less than or equal to ten, and it being understood that the sum m8+m9 is greater than 0 and less than or equal to ten.
[0066] According to another specific aspect of the present invention, said active composition (C) as defined above additionally comprises:
4)—up to 5 mol % of a composition (C VI ) comprising, per 100 mol %:
α)—from 60 mol % to 100 mol % of a compound of formula (VI):
[0000] R2-(—CH 2 —CH 2 —O—) m10 —H (VI),
[0000] in which R2 represents a linear or branched alkyl radical comprising 12 carbon atoms and m10 is an integer of greater than or equal to zero and less than or equal to ten;
β)—optionally up to 40 mol % of a compound of formula (VI′):
[0000] R′ 2 —(—CH 2 —CH 2 —O—) m10 —H (VI′),
[0000] in which R′ 2 represents a linear or branched alkyl radical comprising 14 carbon atoms and m10 is an integer of greater than or equal to zero and less than or equal to ten; and
γ)—optionally up to 10 mol % of a compound of formula (VI″):
[0000] R″ 2 —(—CH 2 —CH 2 —O—) m10 —H (VI″),
[0000] in which R″ 2 represents a linear or branched alkyl radical comprising 16 carbon atoms and m10 is an integer of greater than or equal to zero and less than or equal to ten.
[0071] According to a specific aspect of the present invention, said surfactant composition (C) as defined above comprises:
1)—a proportion of greater than or equal to 20 mol % and of less than or equal to 50 mol % of a composition (C II ) as defined above; 2)—a proportion of greater than or equal to 50 mol % and of less than or equal to 80 mol % of a composition (C III ) as defined above.
[0074] According to another specific aspect of the present invention:
1)—said composition (C II ) comprises, per 100 mol %:
α)—from 60 mol % to 80 mol % of the compound of formula (II), β)—from 15 mol % to 30 mol % of the compound of formula (II′), and γ)—up to 10 mol % of the compound of formula (II″), and
2)—said composition (C III ) comprises, per 100 mol %:
α)—from 60 mol % to 80 mol % of the compound of formula (III), of its isomer of formula (IV) or of the mixture of these isomers, β)—from 15 mol % to 30 mol % of the compound of formula (III′), of its isomer of formula (IV′) or of the mixture of these isomers, and γ)—up to 10 mol % of the compound of formula (III″), of its isomer of formula (IV″) or of the mixture of these isomers.
[0083] Another subject matter of the invention is a process for the preparation of said surfactant composition (C) as defined above, characterized in that it comprises the following successive stages:
[0000] a stage a) of reaction of a mixture of alcohols comprising, per 100 mol %:
from 60 mol % to 100 mol % of a compound of formula (VII),
[0000] R2-O—H (VII),
[0000] in which R2 represents a linear or branched alkyl radical comprising 12 carbon atoms;
optionally up to 40 mol % of a compound of formula (VII′):
[0000] R′ 2 —O—H (VII′),
[0000] in which R′ 2 represents a linear or branched alkyl radical comprising 14 carbon atoms, and
optionally up to 10 mol % of a compound of formula (VI″):
[0000] R″ 2 —O—H (VII″),
[0000] in which R″ 2 represents a linear or branched alkyl radical comprising 16 carbon atoms;
with a stoichiometric excess of 3-(hydroxymethyl)-3-ethyloxetane of formula (VIII):
[0000]
[0000] in order to form a composition (C′) comprising the compound of formula (IX):
[0000]
[0000] in which R2 is as defined above;
optionally the compound of formula (IX′):
[0000]
[0000] in which R′ 2 is as defined above;
optionally the compound of formula (IX″):
[0000]
[0000] in which R″ 2 is as defined above;
the compound of formula (X):
[0000]
[0000] or its isomer of formula (XI):
[0000]
[0000] or a mixture of these two isomers;
in which compounds of formulae (X) and (XI) R2 is as defined above;
optionally the compound of formula (X′):
[0000]
[0000] or its isomer of formula (XI′):
[0000]
[0000] or a mixture of these two isomers;
in which compounds of formulae (X′) and (XI′) R′ 2 is as defined above;
optionally the compound of formula (X″):
[0000]
[0000] or its isomer of formula (XI″):
[0000]
[0000] or a mixture of these two isomers;
in which compounds of formulae (X″) and (XI″) R″ 2 is as defined above;
a stage b) of reaction, in the desired stoichiometric ratio, of said composition (C′) with ethylene oxide of formula (XII):
[0000]
[0000] in order to form said surfactant composition (C).
[0084] Another subject matter of the invention is the intermediate composition C′ of the process as defined above.
[0085] Another subject matter of the invention is the intermediate compounds of formulae (IX), (X) and (XI) of the process as defined above.
[0086] A final subject matter of the invention is the use of the surfactant composition (C) as defined above as emulsifying agent of oil-in-water (O/W) type and more particularly as emulsifying agent of oil-in-water (O/W) type, more particularly as inverting agent for a self-invertible inverse latex, alone or as a mixture with other emulsifying agents capable of preparing and intended to prepare an emulsifying system (S 2 ) of oil-in-water (O/W) type.
DETAILED DESCRIPTION OF THE INVENTION
[0087] The term “self-invertible inverse latex” denotes a water-in-oil emulsion of a crosslinked polymer, obtained by inverse emulsion polymerization of the monomers employed, said water-in-oil emulsion of a polymer being capable, by virtue of the presence within it of an emulsifying system (S 2 ) of oil-in-water (O/W) type, said inverting agent, of inverting to give an oil-in-water emulsion by simple dispersion in water with slow mechanical stirring, thus bringing about the thickening of this aqueous phase.
[0088] An example of a self-invertible inverse latex which can advantageously comprise the surfactant composition (C) as defined above, within the (S 2 ) of oil-in-water (O/W) type, is, for example, a composition comprising, per 100% by weight:
a) from 20% by weight to 80% by weight of a crosslinked and/or branched anionic polyelectrolyte (P) obtained by polymerization:
of at least one neutral monomer chosen in particular from acrylamide, N,N-dimethylacrylamide, N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]propenamide [or tris(hydroxymethyl)acrylamidomethane or N-[tris(hydroxymethyl)methyl]acrylamide, also known as THAM] or 2-hydroxyethyl acrylate; and/or of at least one monomer comprising a strong acid functional group; and/or of at least one monomer comprising a weak acid functional group; and/or of at least one neutral monomer of formula (I):
[0000]
in which the R1 radical represents a linear or branched aliphatic radical comprising from 8 to 20 carbon atoms and n represents an integer of greater than or equal to one and less than or equal to thirty;
b) from 5% by weight to 10% by weight of an emulsifying system (S 1 ) of water-in-oil (W/O) type;
c) from 1% by weight to 10% by weight of an emulsifying system (S 2 ) of oil-in-water (O/W) type comprising a non-zero proportion by weight of said surfactant composition (C) as defined above;
d) from 5% by weight to 45% by weight of at least one oil, and
e) from 0% by weight to 45% by weight of water.
[0102] The term “saturated or unsaturated and linear or branched aliphatic radical comprising from 6 to 20 carbon atoms” denotes, for the R1 radical in the formula (I) as defined above, more particularly the linear radicals, such as, for example, the hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl or eicosyl radicals.
[0103] In the composition as defined above, the emulsifying system (S 1 ) of water-in-oil (W/O) type is composed either of just one surfactant or of a mixture of surfactants, provided that said surfactant or said mixture has an HLB value which is sufficiently low to bring about water-in-oil emulsions. An emulsifying agent of water-in-oil type is, for example, sorbitan esters, such as sorbitan oleate, such as that sold by Seppic under the name Montane™ 80, sorbitan isostearate, such as that sold by Seppic under the name Montane™ 70, or sorbitan sesquiolate, such as that sold by Seppic under the name Montane™ 83. There are also some polyethoxylated sorbitan esters, for example pentaethoxylated sorbitan monooleate, such as that sold by Seppic under the name Montanox™ 81, or pentaethoxylated sorbitan isostearate, such as that sold under the name Montanox™ 71 by Seppic. There is also diethoxylated oleocetyl alcohol, such as that sold under the name Simulsol™ OC 72 by Seppic, polyesters with a molecular weight of between 1000 and 3000, products of the condensation between a polyisobutenyl succinic acid or its anhydride, such as Hypermer™ 2296, sold by Uniqema, or finally block copolymers with a molecular weight of between 2500 and 3500, such as Hypermer™ B246, sold by Uniqema, or Simaline™ IE 200, sold by Seppic.
[0104] In the context of this use, the surfactant composition (C) as defined above can be employed, alone or as a mixture with at least one other emulsifying agent of oil-in-water (O/W) type, within said emulsifying system (S 2 ) of oil-in-water (O/W) type, inverting agent for self-invertible inverse latexes.
[0105] According to a specific form of the self-invertible inverse latexes as defined above, the emulsifying system (S 2 ) of oil-in-water (O/W) type consists of 100% by weight of said surfactant composition (C) as defined above.
[0106] According to another specific form of the self-invertible inverse latexes as defined above, the emulsifying system (S 2 ) of oil-in-water (O/W) type additionally comprises at least one emulsifying surfactant of the (O/W) type other than one or other of the compounds constituting said surfactant composition (C) as defined above.
[0107] The term “emulsifying agent of the oil-in-water type” denotes emulsifying agents having an HLB value which is sufficiently high to provide oil-in-water emulsions, such as ethoxylated sorbitan esters, such as sorbitan oleate polyethoxylated with 20 mol of ethylene oxide, sold by Seppic under the name Montanox™ 80, sorbitan laurate polyethoxylated with 20 mol of ethylene oxide, sold by Seppic under the name of Montanox™ 20, castor oil polyethoxylated with 40 mol of ethylene oxide, sold under the name Simulsol™ OL 50, decaethoxylated oleodecyl alcohol, sold by Seppic under the name Simulsol™ OC 710, heptaethoxylated lauryl alcohol, sold under the name Simulsol™ P7, decaethoxylated nonylphenol, sold by Seppic under the name Nonarox™-10-30, or polyethoxylated sorbitan hexaoleates, sold by Seppic under the name Simaline™ IE 400.
[0108] According to a more particular form of the self-invertible inverse latexes as defined above, the emulsifying system (S 2 ) of oil-in-water (O/W) type additionally comprises a non-zero proportion by weight of at least one emulsifying agent of the oil-in-water type chosen from sorbitan oleate polyethoxylated with 20 mol of ethylene oxide, sorbitan laurate polyethoxylated with 20 mol of ethylene oxide, castor oil polyethoxylated with 40 mol of ethylene oxide, decaethoxylated oleodecyl alcohol, heptaethoxylated lauryl alcohol, decaethoxylated nonylphenol or polyethoxylated sorbitan hexaoleates. According to this specific form, said emulsifying system (S 2 ) comprises at least 30% by weight of said mixture (M) as defined above.
[0109] According to a very specific form of the self-invertible invert latexes as defined above, the emulsifying system (S 2 ) of oil-in-water type comprises, per 100% of its weight:
from 10% by weight to 40% by weight of heptaethoxylated lauryl alcohol and from 60% by weight to 90% by weight of the surfactant composition (C) as defined above.
[0112] The term “crosslinked polyelectrolyte” denotes, for (P), a non-linear polyelectrolyte which is provided in the form of a three-dimensional network insoluble in water but swellable with water and which thus results in a chemical gel being obtained.
[0113] The term “branched polyelectrolyte” denotes, for (P), a non-linear polymer which has pendent chains, so as to obtain, when this polymer is dissolved in water, a high state of entanglement, resulting in very high viscosities with a low gradient.
[0114] The polyelectrolyte (P) is more particularly crosslinked with a diethylenic or polyethylenic compound in the molar proportion, expressed with respect to the monomers employed, of generally less than or equal to 0.40 mol %, mainly of less than 0.25 mol %, more particularly of less than or equal to 0.05 mol % and very particularly of between 0.005 mol % and 0.01 mol %. Preferably, the crosslinking agent and/or the branching agent is chosen from ethylene glycol dimethacrylate, diethylene glycol diacrylate, sodium diallyloxyacetate, ethylene glycol diacrylate, diallylurea, triallylamine, trimethylolpropane triacrylate, methylenebisacrylamide or a mixture of these compounds.
[0115] Examples of constituent crosslinked polyelectrolytes (P) of said self-invertible inverse latexes include:
crosslinked terpolymers of acrylic acid, partially salified in the sodium salt or ammonium salt form, of acrylamide and of tetraethoxylated lauryl acrylate; crosslinked terpolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, of acrylamide and of tetraethoxylated lauryl acrylate; crosslinked terpolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, of acrylic acid, partially salified in the sodium salt form, and of tetraethoxylated lauryl acrylate; crosslinked terpolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, of 2-hydroxyethyl acrylate and of tetraethoxylated lauryl acrylate; crosslinked copolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, and of tetraethoxylated lauryl acrylate; crosslinked copolymers of acrylic acid, partially salified in the ammonium salt or monoethanolamine salt form, and of tetraethoxylated lauryl acrylate; crosslinked tetrapolymers of acrylamide, of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, of acrylic acid, partially salified in the sodium salt form, and of tetraethoxylated lauryl acrylate; tetrapolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially salified in the sodium salt form, of acrylamide, of vinylpyrrolidone and of tetraethoxylated lauryl acrylate; and crosslinked pentapolymers of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, partially or completely salified in the sodium salt form, of acrylic acid, partially salified in the sodium salt form, of 2-hydroxyethyl acrylate, of tris(hydroxymethyl)aminomethylacrylamide and of tetraethoxylated lauryl acrylate.
[0125] The constituent crosslinked anionic polyelectrolyte (P) of said self-invertible inverse latexes comprises, per 100% of monomers employed, more particularly:
from 20 mol % to 80 mol % of monomer units resulting from a monomer comprising either a strong acid functional group or a weak acid functional group; from 15 mol % to 75 mol % of monomer units resulting from a neutral monomer other than the compound of formula (I) as defined above; from 0.5 mol % to 5 mol % of monomer units resulting from a monomer of formula (I) as defined above.
[0129] According to another specific aspect, the crosslinked anionic polyelectrolyte (P) comprises, per 100% of monomers employed:
from 55 mol % to 80 mol % of monomer units resulting from a monomer comprising a strong acid functional group; from 15 mol % to 40 mol % of monomer units resulting from a neutral monomer other than the compound of formula (I) as defined above; from 1 mol % to 5 mol % of monomer units resulting from a monomer of formula (I) as defined above.
[0133] According to another specific form, said self-invertible inverse latex as defined above comprises more than 60% by weight and at most 70% by weight of anionic polyelectrolyte (P).
[0134] In said self-invertible inverse latexes as defined above, the oil phase is composed either of a commercial mineral oil comprising saturated hydrocarbons, such as paraffins, isoparaffins or cycloparaffins, exhibiting, at ambient temperature, a density between 0.7 and 0.9 and a boiling point of greater than approximately 250° C., such as, for example, Marcol™ 52, sold by Exxon Chemical, or of a vegetable oil, such as squalane of vegetable origin, or a synthetic oil, such as hydrogenated polyisobutene or hydrogenated polydecene, or of a mixture of several of these oils. Marcol™ 52 is a commercial oil corresponding to the definition of liquid paraffins of the Codex français [French Pharmacopeia]. This is a white mineral oil in accordance with the FDA 21 CFR 172.878 and CFR 178.3620 (a) regulations and it is registered in the USA Pharmacopeia, US XXIII (1995), and in the European Pharmacopoeia (1993). The composition as defined above can also comprise various additives, such as complexing agents, chain-transfer agents or chain-limiting agents.
[0135] The aim of the examples which follow is to illustrate the present invention without, however, limiting it.
Example A
Preparation of a Surfactant Composition (C) Employed in the Composition which is a Subject Matter of the Present Invention
Stage A1): Preparation of the Intermediate Composition (C′)
[0136] 21 100 g of a mixture of fatty alcohols, comprising from 65% by weight to 75% by weight of alkanol comprising 12 carbon atoms, from 21% by weight to 28% by weight of alkanol comprising 14 carbon atoms and from 4% by weight to 8% by weight of alkanol comprising 16 carbon atoms, heated beforehand, are introduced into a reactor, are kept stirred and are dried. 326 grams of 50% boron trifluoride in diethyl ether are subsequently added and then 32 600 g of 3-(hydroxymethyl)-3-ethyloxetane are gradually added with stirring over 4 hours, the temperature being maintained at approximately 110° C. The reaction medium is then left at 115° C. for a further 11 hours. The expected composition (C′) is then obtained, which composition is characterized as follows:
Appearance at 25° C.: Cloudy gel Acid number (in mg KOH/g; NFT60-204): 3.9 Hydroxyl number (in mg KOH/g): 400.5 Content by weight of free 2-(hydroxymethyl)-2-ethyloxetane (determined by gas chromatography): <0.05% Content by weight of free alkanols (determined by gas chromatography): C 12 alkanol: 5.7%; C 14 alkanol: 2.0%; C 16 alkanol: 0.5%.
Stage A2): Preparation of the Surfactant Composition (C)
[0142] 50 000 g of the intermediate composition (C′) obtained in the preceding stage A1) are introduced with 75 g of potassium hydroxide into an autoclave with a capacity of 0.1 m 3 and are then dried at a temperature of 105° C. An amount of 35 000 g of ethylene oxide is subsequently gradually introduced while regulating the temperature of the reaction mixture at a value of 125° C. Once the total amount of ethylene oxide has been introduced, the reaction mixture is kept stirred at 125° C. for an additional period of time of one hour. The product then obtained is subsequently cooled to a temperature of 80° C. and emptied out. The surfactant composition (C) is then obtained, which composition is characterized as follows:
Appearance at 30° C.: clear liquid Color: 125 Alpha Hydroxyl number (in mg KOH/g): 252.5 Acid number (in mg KOH/g) (NFT60-204): 0.08 Residual water content: 0.05% Cloud point (NF EN 1890E): 76° C. Content by weight of free alkanols (gas chromatography): C 12 alkanol: 1.2%; C 14 alkanol: 0.4%; C 16 alkanol: 0.1%, i.e., in total, 1.7% of residual alkanols Viscosity at 25° C. (Brookfield LVT, Rotor 3, Speed 12): 1 072 mPa·s
Example 1 (According to the Invention)
Self-Invertible Inverse Latex of the ATBS (Na Salt)/HEA/(LA-4EO) [ATBS/HEA/(LA-4EO) 89.0/9.9/1.1 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0000]
a)—The following are successively introduced with stirring into a first beaker:
672.5 g of a 55% by weight commercial solution of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (ATBS Na), 20.8 g of 2-hydroxyethyl acrylate (HEA); 0.028 g of methylenebisacrylamide (MBA); and 1.0 g of a 40% by weight commercial solution of sodium diethylenetriaminepentaacetate.
[0156] The pH is then adjusted to 4 therein by adding, if necessary, the required amounts of 2-acrylamido-2-methylpropanesulfonic acid and deionized water up to 700 g.
b)—The following are successively introduced with stirring into a second beaker:
130 g of polyisobutene, 30 g of Marcol™ 52, 90 g of Isopar™ H, 17 g of Montane™ 70, 3 g of Hypermer™ 6212, 5 g of Simaline™ IE 200, 7.2 g of tetraethoxylated lauryl acrylate (commercial) (LA-4EO), 0.36 g of dilauroyl peroxide
c)—The aqueous phase is then incorporated in the organic phase with stirring and then the preemulsion thus obtained is subjected to shearing mechanical stirring using a rotor agitator of Silverson type so as to create a fine emulsion while sparging with nitrogen. d)—After cooling to approximately 8° C., the polymerization reaction is initiated using the oxidation/reduction couple: cumene hydroperoxide/sodium metabisulfite. e)—Once the polymerization reaction is complete, the Isopar™ H and virtually all of the water are removed by vacuum distillation. f)—After introduction of 2% by weight of Laureth-7 and 4% by weight of the surfactant composition (C) obtained in example A, the self-invertible inverse latex (1) is obtained, which latex comprises approximately 63% of polymer, which is not very viscous, which inverts very rapidly in water and which has a high thickening power. Furthermore, this inverse latex is very stable as no phenomenon of syneresis is observed, in that only a very small amount of oil is released and that polymer does not sediment out. Its water content, measured by Karl-Fischer titrimetry, is 1.8% by weight.
2) Viscosity Measurements
[0000]
a)—The viscosity of the self-invertible inverse latex (1) obtained as indicated in section 1, that of an aqueous solution devoid of sodium chloride (Sol.1) and those of aqueous solutions respectively comprising 0.1% by weight (Sol.2) and 1% by weight (Sol.3) of sodium chloride are measured, said aqueous solutions each comprising 2% by weight of said self-invertible inverse latex (1). The results measured using a Brookfield RVT viscometer are recorded in the following table:
[0000]
Rotor (R);
Rotational speed of the
Viscosity
rotor (S)
(in
(in revolutions per minute)
mPa · s)
Inverse latex
R 3, S 20
2700
(1)
Sol. 1
R 6, S 5
54 000
Sol. 2
R 6, S 5
27 000
Sol. 3
R 3, S 5
1600
3) Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex
[0000]
a)—The inversion time is evaluated by measuring the time necessary to obtain a smooth and homogeneous gel for a 2% by weight aqueous solution of self-invertible inverse latex (1) under the standard conditions for measuring this viscosity, that is to say by incorporating 16 g of the inverse latex (1) in 784 g of water, the combined mixture being placed in a 1 liter low-form beaker, and by then stirring the combined mixture using a butterfly-type axial-flow impeller rotating at 150 revolutions per minute. The inversion time is thus a period of time evaluated between starting the stirrer and the appearance of a smooth and homogeneous medium in the beaker. In the present example, the inversion time is 50 seconds.
b)—The stability of the inverse latex is evaluated by observing the time for appearance of an oil layer at the surface. In the present example, the time for appearance of the oil layer at the surface of the inverse latex (1) is two weeks.
Example T1 (According to the State of the Art)
Self-Invertible Inverse Latex of the ATBS(Na Salt)/HEA/(LA-4EO) [ATBS/HEA/(LA-4EO) 89.0/9.9/1.1 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0173] Stages a) to d) of example 1 are reproduced. In stage f), 4% by weight of Montanox™ 20 are added in place of 4% by weight of the surfactant composition (C) and the self-invertible inverse latex (T1) is obtained.
2) Viscosity Measurements
[0000]
a)—The viscosity of the self-invertible inverse latex (T1) obtained as indicated in section 1, that of an aqueous solution devoid of sodium chloride (Sol.4) and those of aqueous solutions respectively comprising 0.1% by weight (Sol.5) and 1% by weight (Sol.6) of sodium chloride are measured, said aqueous solutions each comprising 2% by weight of said self-invertible inverse latex (T1). The results measured using a Brookfield RVT viscometer are recorded in the following table:
[0000]
Rotor (R);
Rotational speed of the
rotor (S)
Viscosity
(in revolutions per
(in
minute)
mPa · s)
Inverse latex
R 3, S 20
2900
(T1)
Sol. 4
R 6, S 5
51 200
Sol. 5
R 6, S 5
25 200
Sol. 6
R 3, S 5
1300
3) Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex
[0000]
a)—The inversion time, evaluated in the same way as in the preceding example, is 2 minutes 20 seconds.
b)—The stability of the inverse latex (T1) is evaluated in the same way as in the preceding example. Significant release of oil is observed after one week.
Example 2 (According to the Invention)
Self-Invertible Inverse Latex of the ATBS(Na Salt)/HEA/(LA-4EO) [ATBS/HEA/(LA-4EO) 89.0/9.9/1.1 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0177] Stages a) to d) of example 1 are reproduced. In stage f), only 4% by weight of the surfactant composition (C) are added and the self-invertible inverse latex (2) is obtained.
2) Viscometry, Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex (2)
[0000]
a)—The viscometric performance of the inverse latex (2) is similar to that reported for the inverse latex of example 1.
b)—The inversion time of the inverse latex (2), evaluated in the same way as in example 1, is approximately 40 seconds.
c)—The stability of the inverse latex (2) is evaluated in the same way as in example 1. The time for the appearance of the oil layer is a few days.
Example T2 (According to the State of the Art)
Self-Invertible Inverse Latex of the ATBS(Na Salt)/HEA/(LA-4EO) [ATBS/HEA/(LA-4EO) 89.0/9.9/1.1 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0181] Stages a) to d) of example 1 are reproduced. In stage f), 4% by weight of a composition (C″′) are added, which composition comprises, per 100 mol %:
i) a proportion of greater than or equal to 10 mol % and less than or equal to 50 mol % of a compound of formula (II″′) corresponding to the formula (II) in which R2 represents a linear or branched alkyl radical comprising 10 carbon atoms and in which the sum m1+m2+m3 is equal to 5; ii) a proportion of greater than or equal to 50 mol % and less than or equal to 90 mol % of a compound of formula (III″′) or of its isomer of formula (IV″′) or of the mixture of these two isomers, formulae (III″′) and (IV″′) respectively corresponding to the formulae (III) and (IV) in which R2 represents a linear or branched alkyl radical comprising 10 carbon atoms and in which the sum m4+m5+m6+m7 is equal to 5;
and the self-invertible inverse latex (T2) is obtained.
2) Viscometry, Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex (T2)
[0000]
a)—The viscometric performance of the inverse latex (T2) is similar to that reported for the inverse latex of example 1.
b)—The inversion time of the inverse latex (T2), evaluated in the same way as in example 1, is approximately 50 seconds.
c)—The stability of the inverse latex (T2) is evaluated in the same way as in example 1. The time for appearance of the oil layer is a few hours.
Example T3 (According to the State of the Art)
Self-Invertible Inverse Latex of the AM/AA/(LA-4EO) [AM/AA/(LA-4EO) 24.7/74.1/1.2 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0000]
a)—The following are successively introduced with stirring into a first beaker:
106.5 g of a 50% (by weight) commercial solution of acrylamide (AM), 162.0 g of glacial acrylic acid (AA), 98.1 g of a 29.3% by weight aqueous ammonia solution, 0.047 g of methylenebisacrylamide (MBA), 0.45 g of a 40% commercial solution of sodium diethylenetriaminepentaacetate, deionized water up to 680 g.
b)—The following are successively introduced with stirring into a second beaker:
121 g of polyisobutene, 28 g of Marcol™ 52, 99 g of Isopar™ H, 17 g of Montane™ 70, 3 g of Hypermer™ 2296, 5 g of Simaline™ IE 200, 1.2 g of tetraethoxylated lauryl acrylate (commercial) (LA-4EO), 0.1 g of AIBN.
c)—The aqueous phase is then incorporated in the organic phase with stirring and then the preemulsion thus obtained is subjected to shearing mechanical stirring using a rotor agitator of Silverson type so as to create a fine emulsion while sparging with nitrogen.
d)—After cooling to approximately 8° C., the polymerization reaction is initiated using the oxidation/reduction couple: cumene hydroperoxide/sodium metabisulfite.
e)—Once the polymerization reaction is complete, the Isopar™ H and virtually all of the water are removed by vacuum distillation.
f). After introduction of 4% of Montanox™ 20 and 2% of Laureth-7, the self-invertible inverse latex (T3) is obtained, which latex comprises approximately 63% of polymer, which is not very viscous, which inverts very rapidly in water and which has a high thickening power. Its water content, measured by Karl-Fischer titrimetry, is 1.8% by weight.
2) Viscosity Measurements
[0000]
a)—The viscosity of the self-invertible inverse latex (T3) obtained as indicated in section 1, that of an aqueous solution devoid of sodium chloride (Sol.7) and those of aqueous solutions respectively comprising 0.1% by weight (Sol.8) and 1% by weight (Sol.9) of sodium chloride are measured, said aqueous solutions each comprising 2% by weight of said self-invertible inverse latex (T3). The results measured using a Brookfield RVT viscometer are recorded in the following table:
[0000]
Rotor (R);
Rotational speed of the
Viscosity
rotor (S)
(in
(in revolutions per minute)
mPa · s)
Inverse latex
nd
(T3)
Sol. 7
R 6, S 5
79 400
Sol. 8
R 6, S 5
45 200
Sol. 9
R 3, S 5
3300
nd: not determined
3) Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex (T3)
[0000]
b)—The inversion time of the inverse latex (T3), evaluated in the same way as in example 1, is approximately 2 minutes.
c)—The stability of the inverse latex (T3) is evaluated in the same way as in example 1. The time for appearance of the oil layer is two weeks.
Example 3 (According to the Invention)
Self-Invertible Inverse Latex of the AM/AA/(LA-4EO) [AM/AA/(LA-4EO) 24.7/74.1/1.2 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0210] Stages a) to d) of example T3 are reproduced. In stage f), 2% by weight of Laureth-7 and 4% by weight of the surfactant composition (C) are added in place of the 4% of Montanox™ 20 and 2% of Laureth-7 of said example T3 and the self-invertible inverse latex (3) is obtained.
2) Viscometry, Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex (3)
[0000]
a)—The viscometric performance of the inverse latex (3) is similar to that reported for the inverse latex of example T3.
b)—The inversion time of the inverse latex (3), evaluated in the same way as in example 1, is approximately 30 seconds.
c)—The stability of the inverse latex (3) is evaluated in the same way as in example 1. The time for appearance of the first oil drops is three weeks.
Example 4 (According to the Invention)
Self-Invertible Inverse Latex of the ATBS (Na Salt)/AA/HEA/THAM/(LA-4EO) [ATBS/AA/HEA/THAM/(LA-4EO) 83.9/1.9/9.3/3.7/1.2 Molar] Copolymer Crosslinked with MBA
1) Preparation
[0000]
a)—The following are successively introduced with stirring into a first beaker:
672.5 g of a 55% (by weight) commercial solution of the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (ATBS Na); 20.8 g of 2-hydroxyethyl acrylate; 12.6 g of THAM; 2.6 g of acrylic acid (AA); 0.041 g of methylenebisacrylamide (MBA); 0.45 g of a 40% commercial solution of sodium diethylenetriaminepentaacetate.
[0221] The pH is then adjusted therein to 4 by adding, if necessary, the required amount of 2-acrylamido-2-methylpropanesulfonic acid and deionized water up to 700 g.
b)—The following are successively introduced with stirring into a second beaker:
130 g of polyisobutene, 30 g of Marcol™ 52, 90 g of Isopar™ H, 17 g of Montane™ 70, 5 g of Hypermer™ 6212, 3 g of Dehymuls PGPH (polyglyceryl polyhydroxystearate), 7.4 g of tetraethoxylated lauryl acrylate (commercial) (LA-4EO), 0.14 g of dilauroyl peroxide.
c)—The aqueous phase is then incorporated in the organic phase with stirring and then the preemulsion thus obtained is subjected to shearing mechanical stirring using a rotor agitator of Silverson type so as to create a fine emulsion while sparging with nitrogen. d)—After cooling to approximately 8° C., the polymerization reaction is initiated using the oxidation/reduction couple: cumene hydroperoxide/sodium metabisulfite. e)—Once the polymerization reaction is complete, the Isopar™ H and virtually all of the water are removed by vacuum distillation. f)—After introduction of 2% by weight of Laureth-7 and 4% by weight of the surfactant composition (C) obtained in example A, the self-invertible inverse latex (4) is obtained, which latex comprises approximately 63% of polymer, which is not very viscous, which inverts very rapidly in water and which has a high thickening power. Its water content, measured by Karl-Fischer titrimetry, is 2.2% by weight.
2) Viscosity Measurements
[0000]
a)—The viscosity of the self-invertible inverse latex (4) obtained as indicated in section 1, that of an aqueous solution devoid of sodium chloride (Sol.10) and that of an aqueous solution comprising 0.1% by weight (Sol.11) of sodium chloride are measured, said aqueous solutions each comprising 2% by weight of said self-invertible inverse latex (4). The results, measured using a Brookfield RVT viscometer, are recorded in the following table:
[0000]
Rotor (R);
Rotational speed of the
Viscosity
rotor (S)
(in
(in revolutions per minute)
mPa · s)
Inverse latex
R 3, S 20
1100
(4)
Sol. 10
R 6, S 5
66 200
Sol. 11
R 6, S 5
16 500
nd: not determined
3) Measurement of the Inversion Time and Evaluation of the Stability of the Inverse Latex
[0000]
b)—The inversion time of the inverse latex (4), evaluated in the same way as in example 1, is approximately 30 seconds.
c)—The stability of the inverse latex (4) is evaluated in the same way as in example 1. The time for appearance of the first oil drops is three weeks.
|
The invention relates to a novel composition made of polyalkoxylated derivatives of trimethylolpropane and fatty alcohols, said composition lending itself to the preparation thereof and to the use thereof as a reversing agent for a reversible reverse latex.
| 2
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This is a Continuation of application Ser. No. 08/409,585 filed Mar. 24, 1995 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an image reading apparatus for two-dimensionally reading an image with line sensors, and more particularly to an image reading apparatus whose resolution has been increased without increasing the number of photoelectric transducers of line sensors.
2. Description of the Related Art
There have widely been used image reading apparatuses including photomultipliers or charge-coupled devices (CCDs) for reading an image on a document to generate an image signal. Since the image reading apparatuses divide an image into a finite number of pixels and read image information from the pixels, there is a certain limitation on the spatial frequencies of images that can be reproduced from image information read by the image reading apparatus.
If an image is read using a photomultiplier, then it is possible to increase the resolution of the read image by increasing the frequency of a synchronizing signal used in the reading process.
If an image is read using a CCD, however, then since the number of pixels of a produced image signal is limited by the number of the photoelectric transducers included in the CCD and also since the area of the photosensitive section of the CCD is limited depending on the areas of the photoelectric transducers, the resolution of the CCD is lower than the photomultiplier. Specifically, the spatial frequency of an image that can be reproduced by a CCD is 1/2P (Nyquist frequency) where P is the distance between the centers of photoelectric transducers, and any spatial frequencies higher than 1/2P give rise to noise.
When images having a spatial frequency in the vicinity of 1/2P are read by a CCD, the CCD responds largely differently depending on the phase of the images with respect to the photoelectric transducers even if the images are the same as each other. For example, as shown in FIG. 12 of the accompanying drawings, when identical sinusoidal images A, B which are 90° out of phase with each other with respect to photoelectric transducers P1, P2, . . . of a CCD are read by the CCD, an image signal generated by the CCD is not representative of the images A, B because the images applied to each of the photoelectric transducers P1, P2, . . . are averaged. FIG. 13 of the accompanying drawings shows the relationship between the spatial frequency and the CCD response at the time the CCD reads identical sinusoidal images that are 20° out of phase with each other. FIG. 13 indicates that the CCD response with respect to the phase differs largely as the spatial frequency is higher. An image reading apparatus known as a scanner for producing film plates for use in printing outputs images at high magnification ratios. In such an image reading apparatus, images having higher spatial frequencies are largely affected by response differences due to phase differences, and such response differences appear as moire patterns, for example, in the outputted images.
Japanese laid-open patent publication No. 3-236687 discloses an attempt to solve such a problem. According to the disclosed arrangement, a solid-state imaging device composed of an area sensor is displaced in four directions, i.e., upward, downward, leftward, and rightward, and pixel signals generated by the solid-state imaging device in these respective four positions are arranged in a given sequence for thereby increasing the apparent number of pixels of the solid-state imaging device, thereby increasing the resolution.
The solid-state imaging device comprises an area sensor, and pixel signals generated by the solid-state imaging device in respective four positions are stored in respective four image buffers and subsequently need to be combined in an image synthesis memory. Therefore, a considerably large memory capacity is required for these memories. The area sensor suffers a structural limitation which makes it difficult to provide a higher resolution than line sensors. It has been impossible to remove effects which the phase has on the image at higher spatial frequencies in the area sensor.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an image reading apparatus which does not need a large memory capacity, is capable of easily carrying out a moving average processing on odd- and even-numbered pixel signal from line sensors, and of generating an image signal of desired resolution irrespective of the number of photoelectric transducers of the line sensors.
To achieve the above object, there is provided in accordance with the present invention an image reading apparatus comprising a line sensor composed of an array of photoelectric transducers for producing pixel signals, memory means for storing the pixel signals produced by the photoelectric transducers, processing means for determining a moving average of the pixel signals stored by the memory means, displacing means for displacing the line sensor in a direction along the array of photoelectric transducers to successive positions each by an interval M expressed by:
M=2P/(2 k+1)
where P is the distance between the centers of adjacent two of the photoelectric transducers and k is an integer of at least 1, and pixel signal combining means for combining the pixel signals produced by the photoelectric transducers when the line sensor is in an original position and displaced from the original position to the successive positions, in a predetermined sequence, and storing the combined pixel signals as a series of data in the memory means.
The memory means may comprise a line buffer for storing as many pixel signals as (2k+1) times the number of the photoelectric transducers.
In the image reading apparatus, the line sensor reads an image when it is in the original position, and stores produced pixel signals in the memory means. Then, the line sensor is displaced successively by the interval M along the array of photoelectric transducers. Each time the line sensor is displaced, it reads the image on the same scanning line, and stores produced pixel signals in the memory means. Such a process is repeated 2k times. Therefore, the image is read in slightly different positions on the same scanning line repeatedly (2k+1) times.
The pixel signals read by the line sensor when it is in the original position and the successive positions displaced therefrom are combined into a predetermined sequence by the pixel signal combining means, and stored as a series of data in the memory means. The pixel signals thus stored in the memory means are subjected to a moving average processing to produce an image signal that is composed of as many moving average pixel signals as (2k+1) times the number of the photoelectric transducers of the line sensor.
Consequently, the image signal produced by the image reading apparatus has a resolution (2k+1) times larger than that of an image signal which would otherwise be produced if an image were read by a CCD line sensor fixed against displacement. Since the resolution is (2k+1) times larger, the spatial frequency that can be reproduced is also (2k+1) times higher. Therefore, an image can be reproduced from the image signal without being affected by the phase of the original image.
The above and other objects, features, and advantages of the present invention will become apparent from the following description when taken in conjunction with the accompanying drawings which illustrate preferred embodiments of the present invention by way of example.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram, partly in perspective, of an image reading apparatus according to the present invention;
FIG. 2 is a block diagram, partly in elevation, of the image reading apparatus;
FIG. 3 is a cross-sectional view of a transducer assembly of the image reading apparatus;
FIG. 4 a side elevational view of the transducer assembly of the image reading apparatus;
FIG. 5 is an enlarged fragmentary cross-sectional view of the transducer assembly shown in FIG. 3;
FIG. 6 is a timing chart of a signal processing sequence of the image reading apparatus;
FIG. 7 is a view showing the relationship between displaced positions of CCD line sensors of the image reading apparatus;
FIG. 8 is a graph showing the relationship between the spatial frequency and the response of the image reading apparatus;
FIG. 9 is a side elevational view of a position adjusting mechanism of the transducer assembly of the image reading apparatus;
FIG. 10 is a cross-sectional view of the position adjusting mechanism of the transducer assembly of the image reading apparatus;
FIG. 11 is a fragmentary perspective view of another transducer assembly for use in the image reading apparatus;
FIG. 12 is a diagram showing the relationship between the phases of images and photoelectric transducers of a CCD line sensor of a conventional image reading apparatus; and
FIG. 13 is a graph showing the relationship between the spatial frequency and the response of the conventional image reading apparatus.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIGS. 1 and 2, an image reading apparatus 10 according to the present invention generally comprises an illuminating light source 12 for illuminating a subject S in a main scanning direction indicated by the arrow Y while the document S is being fed in an auxiliary scanning direction indicated by the arrow X, a condensing lens 14 for concentrating illuminating light L that has passed through the subject S, a transducer assembly 16 for converting the illuminating light L concentrated by the condensing lens 14 into an electric signal, and a signal processor 18 for processing the electric signal from the transducer assembly 16.
As shown in FIGS. 3 and 4, the transducer assembly 16 comprises a support base 20 elongate in the main scanning direction Y, an oscillatory base 22 supported by the support base 20 for oscillating movement in the main scanning direction Y with respect to the support base 20, a plurality of stacked prisms 26b, 26g, 26r fixed to the oscillatory base 22 by a bracket 24, and a plurality of CCD line sensors 28b, 28g, 28r fixed respectively to the prisms 26b, 26g, 26r.
The support base 20 has an elongate opening 30 defined centrally therein for passing the illuminating light L therethrough to the CCD line sensors 28b, 28g, 28r, a hole 34 defined in one end thereof and receiving a piezoelectric element 32 that serves as a displacing means, and a hole 38 defined in the opposite end thereof and receiving a coil spring 36.
The oscillatory base 22 has an elongate opening 40 defined centrally therein in substantial alignment with the opening 30 in the support base 20, and has opposite ends positioned at respective inner ends 34a, 38a of the holes 34, 38 in the support base 20. The support base 20 and the oscillatory base 22 are integral with each other, but essentially separate from each other by a slit 42 (see also FIG. 5) which extends in the main scanning direction Y and has opposite ends bent in the direction normal to the main scanning direction Y, i.e., in the direction in which the prisms 26b, 26g, 26r are stacked. As shown in FIG. 5, the support base 20 has slits 44a, 44b defined therein closely and parallel to the bent ends of the slit 42 between the bent ends of the slit 42 and the opposite ends of the oscillatory base 22, leaving thin walls 46a, 46b between the bent ends of the slit 42 and the slits 44a, 44b. The slits 44a, 44b extend from the stacked prisms 26b, 26g, 26r toward the slit 42, but terminates short of the slit 42. As a consequence, the oscillatory base 22 is allowed by the thin walls 46a, 46b to be displaced in the main scanning direction Y with respect to the support base 20.
The slit 42 communicates with a hole 48 which is defined in one end of the support base 20 for passing therethrough a wire (not shown) for cutting the slit 42 with a wire-cutting electric discharge machine.
The piezoelectric element 32 is mounted in the hole 34 in the support base 20 by a fixing plate 50, and has an end held against the inner end 34a of the hole 34. The coil spring 36 is mounted in the hole 38 in the support base 20 by a screw 52, and has an end held against the inner end 38a of the hole 38.
As shown in FIGS. 3 and 4, the bracket 24 is fastened to the oscillatory base 22 by screws 54. As shown in FIG. 4, the prisms 26b, 26g, 26r are joined to each other through dichroic filters 56a, 56b interposed therebetween. The dichroic filters 56a, 56b serve to separate the illuminating light L into lights B, G, R of different wavelengths and guide the lights B (blue), G (green), R (red) respectively to the CCD line sensors 28b, 28g, 28r. The CCD line sensors 28b, 28g, 28r serve to photoelectrically convert the lights B, G, R into corresponding electric signals B, G, R.
As shown in FIG. 1, the signal processor 18 comprises a B signal processor 58b for processing the B signal from the CCD line sensor 28b, a G signal processor 58g for processing the G signal from the CCD line sensor 28g, a R signal processor 58r for processing the R signal from the CCD line sensor 28r, a piezoelectric signal generator 62 for supplying a drive signal through an amplifier 60 to the piezoelectric element 32, a controller 64 for supplying control signals to the B signal processor 58b, the G signal processor 58g, the R signal processor 58r, and the piezoelectric signal generator 62, a moving average processor 65 for effecting a moving average processing on image signals from the B signal processor 58b, the G signal processor 58g, the R signal processor 58r with respect to pixel signals from odd- and even-numbered photoelectric transducers of the CCD line sensors 28b, 28g, 28r, and an image processor 66 for effecting a desired image processing on the pixel signals from the moving average processor 65.
As shown in FIG. 2, the B signal processor 58b comprises an amplifier 68 for amplifying the pixel signals from the CCD line sensor 28b, two line buffers 70A, 70B each having memory areas that are three times the photoelectric transducers of the CCD line sensor 28b, and a selector switch 72 for selecting the memory areas of the line buffers 70A, 70B. The controller 64 is connected directly to the line buffer 70A, and through an inverter 73 to the line buffer 70B. Each of the G signal processor 58g and the R signal processor 58r is also of the same structure as the B signal processor 58b.
Operation of the image reading apparatus 10 will be described below with reference to FIG. 6.
A subject S with an image recorded thereon is fed in the auxiliary scanning direction X and illuminated by the illuminating light L from the illuminating light source 12 in the main scanning direction Y, so that the subject S is two-dimensionally scanned. The illuminating light L that has passed through the subject S is concentrated by the condensing lens 14, and then separated by the prisms 26b, 26g, 26r and the dichroic filters 56a, 56b into lights B, G, R, which are then applied to the respective CCD line sensors 28b, 28g, 28r.
The controller 64 supplies a line synchronizing signal LSYNC to the piezoelectric signal generator 62 for controlling the transducer assembly 16, and also supplies a selection signal CH and a read/write signal W/R to each of the B signal processor 58b, the G signal processor 58g, the R signal processor 58r for processing image signals.
Specifically, in response to the line synchronizing signal LSYNC from the controller 64, the piezoelectric signal generator 62 supplies a piezoelectric signal P1 of 0 (V) (see FIG. 6) through the amplifier 60 to the piezoelectric element 32. The controller 64 supplies the switching signal CH to the selector switch 72 to connect its terminal T1 to the CCD line buffers 28b, 28g, 28r, and also supplies the read/write signal W/R to the line buffers 70A, 70B of each of the B signal processor 58b, the G signal processor 58g, the R signal processor 58r for placing the line buffer 70A in a WRITE ENABLE state and the line buffer 70B in a READ ENABLE state.
Since the piezoelectric signal P1 is of 0 (V) at this time, the oscillatory base 22 positioned between the coil spring 36 and the piezoelectric element 32 is in an initial non-displaced position S1 (see FIG. 7). Pixel signals a1, a2, a3, . . . generated respectively by the photoelectric transducers of the CCD line sensors 28b, 28g, 28r are transfered to the B signal processor 58b, the G signal processor 58g, the R signal processor 58r, respectively, amplified by the amplifiers 68, and stored through the terminals T1 of the selector switches 72 into 1st, 3rd, 6th, 9th, . . . memory areas of the line buffers 70A of the signal processor 58b, the G signal processor 58g, the R signal processor 58r (see FIG. 2).
Then, in response to the line synchronizing signal LSYNC from the controller 64, the piezoelectric signal generator 62 supplies a piezoelectric signal P2 of α (V) (see FIG. 6) through the amplifier 60 to the piezoelectric element 32. The piezoelectric element 32 is now expanded (or contracted) to displace the oscillatory base 22 in the main scanning direction Y by a distance corresponding to a 2/3 pixel interval of the photoelectric transducers of the CCD line sensors 28b, 28g, 28r. The CCD line sensors 28b, 28g, 28r are now in a position S2 (see FIG. 7) which is displaced the 2/3 pixel interval from the initial position S1. At this time, the controller 64 supplies the switching signal CH to the selector switches 72 to connect the terminals T2 to the respective CCD line sensors 28b, 28g, 28r. Pixel signals b1, b2, b3, . . . generated respectively by the photoelectric transducers of the CCD line sensors 28b, 28g, 28r are transfered to the B signal processor 58b, the G signal processor 58g, the R signal processor 58r, respectively, amplified by the amplifiers 68, and stored through the terminals T2 of the selector switches 72 into 2nd, 5th, 8th, . . . memory areas of the line buffers 70A of the signal processor 58b, the G signal processor 58g, the R signal processor 58r.
Thereafter, in response to the line synchronizing signal LSYNC from the controller 64, the piezoelectric signal generator 62 supplies a piezoelectric signal P2 of β (V) (see FIG. 6) through the amplifier 60 to the piezoelectric element 32. The piezoelectric element 32 is further expanded (or contracted) to displace the oscillatory base 22 in the main scanning direction Y by a distance corresponding to a 4/3 pixel interval of the photoelectric transducers of the CCD line sensors 28b, 28g, 28r. The CCD line sensors 28b, 28g, 28r are now in a position S3 (see FIG. 7) which is displaced the 4/3 pixel interval from the initial position S1. At this time, the controller 64 supplies the switching signal CH to the selector switches 72 to connect the terminals T3 to the respective CCD line sensors 28b, 28g, 28r. Pixel signals c1, c2, c3, -generated respectively by the photoelectric transducers of the CCD line sensors 28b, 28g, 28r are transfered to the B signal processor 58b, the G signal processor 58g, the R signal processor 58r, respectively, amplified by the amplifiers 68, and stored through the terminals T3 of the selector switches 72 into 4th, 7th, 10th, . . . memory areas of the line buffers 70A of the signal processor 58b, the G signal processor 58g, the R signal processor 58r.
In the manner described above, the line buffer 70A of each of the signal processor 58b, the G signal processor 58g, the R signal processor 58r successively stores the pixel signals a1, b1, a2, c1, b2, a3, . . . relative to a first scanning line.
Then, the controller 64 supplies the switching signal CH to the selector switches 72 to connect the terminals T1 to the respective CCD line sensors 28b, 28g, 28r, and also supplies the write/read signal W/R to place the line buffers 70A in a READ ENABLE state and the line buffers 70B in a WRITE ENABLE state. As with the line buffers 70A, the controller 64, while controlling the selector switches 72, controls the piezoelectric signal generator 60 to successively apply the piezoelectric signals P3, P2, P1 to store the pixel signals c1, c2, c3, . . . from the CCD line sensors 28b, 28g, 28r set to the position S3, the pixel signals b1, b2, b3, . . . from the CCD line sensors 28b, 28g, 28r set to the position S2, and the pixel signals a1, a2, a3, . . . from the CCD line sensors 28b, 28g, 28r set to the initial position S1 into the line buffer B of each of the signal processor 58b, the G signal processor 58g, the R signal processor 58r. The piezoelectric signal P2 which is generated after the piezoelectric signal P3 is of a voltage lower than the voltage of a (V) in view of the hysteresis of the piezoelectric element 32.
Consequently, the line buffer 70B of each of the signal processor 58b, the G signal processor 58g, the R signal processor 58r successively stores the pixel signals a1, b1, a2, c1, b2, a3, . . . relative to a second scanning line.
While the line buffer 70B is in the process of storing the pixel signals, the moving average processor 65 reads the pixel signals relative to the first scanning line from the line buffer 70A in the READ ENABLE state, and effects a moving average processing on the read pixel signals. Similarly, while the line buffer 70A is in the process of storing the pixel signals, the moving average processor 65 reads the pixel signals relative to the second scanning line from the line buffer 70B in the READ ENABLE state, and effects a moving average processing on the read pixel signals.
The line buffer 70A alternately store, for example, odd-numbered pixel signals (b1, c1, a3, . . . ) and even-numbered signals (a2, b2, . . . ), except the first pixel signal a1, from corresponding one of the photoelectric transducers of the CCD line sensors 28b, 28g, 28r (see FIGS. 2 and 7). At this time, the moving average processor 65 can determine the average of adjacent pixel signals (b1 and a2, a2 and c1, c1 and b2, . . . ) as a moving average signal. As a result, the moving average processor 65 can produce a moving average signal representing smoothed-out odd- and even-numbered pixel signals from the photoelectric transducers of each of the CCD line sensors 28b, 28g, 28r, using a conventional moving average processing circuit.
The moving average signal outputted from the moving average processor 65 is supplied to the image processor 66 and processed thereby as desired.
The image signal thus produced by the image reading apparatus 10 has a resolution three times larger than that of an image signal which would otherwise be produced if an image were read by the CCD line sensors 28b, 28g, 28r fixed against oscillation. Since the resolution is three times larger, the spatial frequency that can be reproduced is also three times higher. Furthermore, as shown in FIG. 8, the response of the image reading apparatus 10 does not essentially vary depending on the phase of the image with respect to the photoelectric transducers of the CCD line sensors 28b, 28g, 28r. Moreover, because the image signal read by the CCD line sensors 28b, 28g, 28r is representative of one-dimensional data o f each scanning line, each of the buffer memories 70A, 70B is not required to be a large-capacity memory, and hence is highly economical.
In the above embodiment, the CCD line sensors 28b, 28g, 28r are displaced by the 2/3 pixel interval. Gene rally, however, the piezoelectric element 32 may be controlled to vary "n" successively to 0, 1, . . . , 2k in the following equation:
M=2nP/(2k+1)
where M is the displacement from the origin of the CCD line sensors 28b, 28g, 28r in a direction along the CCD arrays, P the distance between the centers of two adjacent photoelectric transducers of the CCD line sensors 28b, 28g, 28r, and k is an integer of 1 or larger.
The image signals read by the CCD line sensors 28b, 28g, 28r which are displaced by the 2/3 pixel interval may be stored in the line buffers 70A and 70B at intervals of M/2 (at n=1), and image signals read by the first and last photoelectric transducers of the respective CCD line sensors, which may not be stored in the buffers 70A, 70B at intervals of M/2 (at n=1), may be respectively stored into the line buffers 70A, 70B at interval of M (at n=1) from the image signals read by adjacent photoelectric transducers and stored in the line buffers.
As shown in FIG. 3, the bracket 24 is coupled to the oscillator base 22 for angularly movement in a scanning plane about a pin 74, and may be adjusted to align the main scanning direction with the direction in which the oscillatory base 22 is displaced by the piezoelectric element 32, for thereby positioning the CCD line sensors 28b, 28g, 28r with respect to the oscillatory base 22. For such an adjustment, as shown in FIG. 9, ribs 76a, 76b extending along the main scanning direction may be mounted on the oscillatory base 22, and the bracket 24 may be positionally adjusted by adjustment screws 78a˜78d threaded through the ribs 76a, 76b and having distal ends abutting against the bracket 24. Furthermore, as shown in FIG. 10, ribs 80a, 80b may be mounted on the opposite ends of the oscillatory base 22 in the main scanning direction, and the prisms 26b, 26g, 26r that have been adjusted through the bracket 24 by the adjustment screws 78a˜78d may be securely held between the ribs 80a, 80b by screws 82a, 82b threaded through the rib 80b and having distal ends abutting against an abutment plate 81 held against an end of the prisms 26b, 26g, 26r.
FIG. 11 shows another transducer assembly for use in the image reading apparatus. In FIG. 11, the transducer assembly comprises a support base 84 and an oscillatory base 86. The support base 84 and the oscillatory base 86 are integral with each other, but essentially separate from each other by various slits 90, 94a, 94b, 98 which are produced by a wire cutting electric discharge machine. The slit 90 is formed by a wire (not shown) inserted in and moving from a hole 88 in the main scanning direction, and then the slits 94a, 94b are formed by wires (not shown) inserted in and moving from respective holes 92a, 92b in the auxiliary scanning direction. Finally, the slit 98, which is of substantially an H shape, is formed by a wire (not shown) inserted in and moving from a hole 96.
As described above, the image reading apparatus 10 according to the present invention does not require a large memory capacity, can easily effect a moving average processing on odd- and even-numbered pixel signal from the line sensors, and can generate an image signal of desired resolution irrespective of the number of photoelectric transducers of the line sensors.
Although certain preferred embodiments of the present invention have been shown and described in detail, it should be understood that various changes and modifications may be made therein without departing from the scope of the appended claims.
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CCD line sensors for detecting R, G, B colors are displaced by a piezoelectric element in a direction in which the CCD line sensors are arrayed, for repeatedly reading an image on one scanning line a plurality of times. Each time the image is read, pixel signals produced by the photoelectric transducers of the CCD line sensors are combined in a given sequence through selector switches, and stored as a series of data in line buffers associated with the colors. Two line buffers are associated with each of the colors. While one of the line buffers is in the process of storing pixel signals, the pixel signals stored in the other line buffer are read and processed into an image signal. The resolution of the image signal is increased without increasing the number of the photoelectric transducers and using a relatively small memory capacity.
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RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 62/295,866, filed on Feb. 16, 2016 entitled “WASTE COLLECTION SYSTEM AND METHOD,” the entirety of which is incorporated by reference herein.
FIELD
[0002] The present inventive concepts relate generally to garbage collection, and more specifically, to the separation of recyclable waste from other garbage at a retail establishment.
BACKGROUND
[0003] Modern stores are environmentally conscious and institute policies or procedures to implement steps to improve the environment.
BRIEF SUMMARY
[0004] In one aspect, provided is a garbage collection system, comprising: a housing positioned under a belt of a point of sale register counter; first and second bins positioned in the housing under the point of sale register counter, the first bin for receiving garbage and/or recyclables, the second bin for receiving hangers; and at least one sliding rail extending perpendicular from a height of the housing, the first and second bins coupled to the at least one sliding rail, at least one of the first and second bins retracting or protruding from at least a portion of the housing in a first position and positioned entirely in the housing in a second position.
[0005] In some embodiments, the housing includes: a first side; a second side; a back wall between the first side and the second side; and an interior between the first side, the second side, and the back wall, wherein the first and second bins are positioned in the interior of the housing.
[0006] In some embodiments, the garbage collection system further comprises a door at an opening to the interior of the housing.
[0007] In some embodiments, the door has at least one of a same or similar color, texture, quality, or material as the sale register counter.
[0008] In some embodiments, the garbage collection system further comprises a pair of sliding rails coupled between the door and the housing, for extending or retracting the door and the first and second bin relative to the housing.
[0009] In some embodiments, the door is hinged to the housing, which when closed, hides the first and second bins in the housing.
[0010] In some embodiments, the garbage collection system further comprises a trash bin housing unit for holding the first and second bins, the trash bin housing unit constructed and arranged for positioning in an interior of the housing.
[0011] In some embodiments, the garbage collection system further comprises a frame for holding the first and second bins, the frame constructed and arranged for positioning in an interior of the housing.
[0012] In some embodiments, the garbage collection system further comprises at least one fixture attachment for coupling the housing to the register counter.
[0013] In some embodiments, the at least one fixture attachment includes a first fixture attachment extending from a top surface of a back wall of the housing.
[0014] In some embodiments, the garbage collection system further comprises the at least one fixture attachment includes a second fixture attachment extending from a surface of a side wall of the housing.
[0015] In some embodiments, the housing is coupled to an underside of the register counter and is suspended above the ground by a predetermined distance.
[0016] In one aspect, provided is a garbage collection system, comprising: a housing positioned under a belt of a point of sale register counter, the housing including a first region for holding a first bin and a second region for holding a second bin; at least one sliding rail extending perpendicular from a height of the housing; and a housing unit or a frame coupled to the at least one sliding rail for holding the first and second bins, the housing unit or frame holding the first and second bins retracting or protruding from at least a portion of the housing in a first position and positioned entirely in the housing in a second position.
[0017] In some embodiments, the first bin is constructed and arranged for receiving at least one of garbage or recyclable material, and the second bin is constructed and arranged for receiving hangers.
[0018] In some embodiments, the housing includes: a first side; a second side; a back wall between the first side and the second side; and an interior between the first side, the second side, and the back wall, wherein the first and second bins are positioned in the interior of the housing.
[0019] In some embodiments, the garbage collection system further comprises a door at an opening to the interior of the housing.
[0020] In some embodiments, the housing is coupled to an underside of the register counter and is suspended above the ground by a predetermined distance.
[0021] In some embodiments, the garbage collection system further comprises a trash bin housing unit for holding the first and second bins, the trash bin housing unit constructed and arranged for positioning in an interior of the housing.
[0022] In some embodiments, the garbage collection system further comprises a frame for holding the first and second bins, the frame constructed and arranged for positioning in an interior of the housing.
[0023] In another aspect, provided is a garbage collection system formed by a process, comprising: positioning a housing under a belt of a point of sale register counter; coupling at least one sliding rail to the register counter, the at least one sliding rail constructed and arranged to extend perpendicular from a height of the housing; coupling a housing unit or a frame coupled to the at least one sliding rail for holding the first and second bins; and retracting or extending the housing unit or frame from at least a portion of the housing in a first position and positioned entirely in the housing in a second position.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0024] The above and further advantages may be better understood by referring to the following description in conjunction with the accompanying drawings, in which like numerals indicate like structural elements and features in various figures. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the concepts.
[0025] FIG. 1A is a perspective view of a garbage collection system in an open position, in accordance with some embodiments.
[0026] FIG. 1B is a perspective view of the garbage collection system of FIG. 1A in a closed position, in accordance with some embodiments.
[0027] FIG. 1C is a top view of the garbage collection system of FIGS. 1A and 1B .
[0028] FIG. 2 is view of an interior of a garbage collection system, in accordance with some embodiments.
[0029] FIGS. 3A and 3B are perspective views of a retail store checkout counter including a garbage collection system in open and closed positions, respectively, in accordance with some embodiments.
DETAILED DESCRIPTION
[0030] One desired procedure by retail establishments is to require store associates to separate garbage from recyclable material such as metal hangers, plastic bags, and so on at a checkout register or other point of sale location.
[0031] FIG. 1A is a perspective view of a garbage collection system 100 A in an open position, in accordance with some embodiments. FIG. 1B is a perspective view of the garbage collection system 100 A of FIG. 1A in a closed position, in accordance with some embodiments. FIG. 1C is a top view of the garbage collection system 100 A of FIGS. 1A and 1B .
[0032] The garbage collection system 110 A may be a self-contained unit, for retrofitting or otherwise installing the entire unit under a register belt area (shown in FIGS. 3A and 3B ). The garbage collection system 100 A includes a housing portion 102 comprising a first side 122 , a second side 123 , and a back wall 124 collectively forming an interior 107 . A door 103 is positioned at an opening to the interior 107 of the housing portion 102 . The door 103 may include a handle 111 for opening and/or closing the door 103 . In a closed position as shown in FIGS. 1B and 1C , the door 103 may abut edges of the first side 122 and 123 , respectively. At least a portion of the door 103 may include a layer or coating of material 108 , such as metal, plastic, or chemical compound, for example, providing a scratch or damage-resistant guard.
[0033] The housing portion 102 and door 103 may be formed of one or more materials sufficient for supporting the weight of garbage bins 112 , 113 and their contents, for example, wood, metal, plastic or related composites, or a combination thereof. The housing portion 102 and/or door 103 may be coated with a material to match the color, texture, material, and/or other features of the checkout counter to which the housing portion 102 is coupled.
[0034] The garbage collection system 100 A may include a rail system, or set of rails 104 , ball bearing slides, or the like, for permitting a trash bin housing unit 115 and door 103 to slide linearly relative to the interior 107 of the housing portion 102 . The rails 104 may be formed of metal and/or other material with withstanding the weight of one or both garbage bins 112 , 113 filled with trash, recyclable material, and so on. The garbage bins 112 , 113 may be positioned in the trash bin housing unit 115 , which turn is positioned on the pair of sliding rails 104 , so that the trash bin housing unit 115 extends and retracts when needed. For example, when retracted, the trash bin housing unit 115 is positioned in the interior 107 of the housing portion 102 . The walls 122 - 124 of the housing portion 102 are attached under a register belt to a checkout counter (see FIGS. 3A and 3B ) which supports the housing portion 102 . When extended, the garbage bins 112 , 113 are exposed so that trash, recyclable materials, and so on may be placed in the garbage bins 112 , 113 . One of the garbage bins 112 , 113 may provide a compartment for holding trash and the other of the bins 112 , 113 may provide a compartment for holding empty hangers and/or other recyclable material. The garbage bins 112 , 113 may be off-the-shelf garbage cans, pails, buckets, or other holding accessory, for example, formed of plastic, stainless steel, or other well-known materials. Although two bins 112 , 113 are shown and described, other embodiments include a single bin, or more than two bins. The bins 112 , 113 may be the same size or be of different sizes.
[0035] FIG. 2 is view of an interior of a garbage collection system 100 B, in accordance with some embodiments. The garbage collection system 100 B may have elements similar to those of the garbage collection system 100 A of FIGS. 1A-1C , which are not repeated due to brevity.
[0036] The garbage collection system 100 B may include components that are different than those described with respect to the garbage collection system 100 A of FIG. 1 . For example, the garbage collection system 100 B can include a wire or metal frame 134 instead of the trash bin housing unit 115 of FIG. 1 . The frame 134 may be formed of metal, plastic, and/or other composite material providing strength and stability for maintaining at least one bin 112 , 113 . In some embodiments, the garbage collection system 100 B has a door 103 positioned in front of the wire frame 134 to cover the garbage bins 112 , 113 when in a closed position, for example, see FIG. 1B . The wire frame 134 may be is positioned on sliding rails 104 or the like, so that the wire frame 134 and the door 103 extend and retract when needed.
[0037] The garbage collection system 100 B includes fixture attachments 131 , 132 , 133 for coupling to a register belt region of a retail store checkout counter. In some embodiments, although not shown, the garbage collection system 100 A of FIG. 1 may include similar or same fixture attachments. In particular, fixture attachment 131 may extend from a top surface of the back wall 124 of the garbage collection system 100 B, fixture attachment 132 can extend from a bottom surface of the first side wall 122 of the garbage collection system 100 B, and fixture attachment 133 can extend from a top surface of the second side wall 133 of the garbage collection system 100 B. Coupling devices such as screws or the like can be used for attaching the fixture attachments 131 , 132 , 133 directly to the register belt region. For example, fixture attachment 131 at a top surface of the back wall 124 may be aligned with a screw hole 109 (see FIG. 1A ) whereby a screw, nail, or other coupling mechanism may be inserted through a hole in the fixture attachment 131 and into the screw hole 109 for securing the fixture attachment 131 to the back wall 124 . Accordingly, when the fixture attachments 131 , 133 abut the underside of the cabinet at which the register belt region is located, and/or a side wall of the register belt region, then the cabinet, or housing portion 102 of the garbage collection system 100 A, 100 B (generally, 100 ) is suspended, i.e., the bottom of the housing portion 102 does not touch the ground. In other embodiments, attachment 132 may be coupled to the bottom of the cabinet so that the housing portion 102 touches the ground, or more specifically, directly abuts the bottom or floor of the cabinet instead of or in addition to the sidewall of the register belt cabinet.
[0038] FIGS. 3A and 3B are perspective views of a retail store checkout counter 16 having a register belt 14 , and further including the garbage collection system 100 A of FIG. 1A-1C or the garbage collection system 100 B of FIG. 2 , or other related garbage collection system under the register belt area 14 , in accordance with some embodiments. In FIG. 3A , the garbage collection system 100 is in a closed or retracted position. In FIG. 3B , the garbage collection system 100 is in an open or extended position.
[0039] The retail store checkout counter 16 may support a plurality of well-known electronic and/or mechanical devices used by a store associate at a checkout counter, for example, but not limited to, a point of sale (POS) terminal or related computer having a display, processor, memory, input/output devices, and so on, optical bar code scanner, printer, electronic payment processing device, cash tray, and credit card processing module (not shown). Elements of the POS device may be positioned on, at, or near a table surface 20 of the checkout counter 16 such as a display monitor 12 , while other elements such as the processor and memory may be positioned below the table surface, for example, collocated in a compartment under the register belt 302 . The garbage collection system 100 may be positioned between the POS system 12 and the register belt 16 , or separate from the POS system 12 by a predetermined distance under the register belt 16 . In other embodiments, the garbage collection system 100 is positioned under the table 20 in such a manner that it does not interfere with other physical elements of a checkout counter 16 such as electronic parts, wires, and so on. In some embodiments, the garbage collection system 100 may include two housing units: a first housing unit under the table 20 and holding a first bin, and a second housing unit under the register belt 14 and holding a second bin.
[0040] The self-contained unit of the garbage collection system 100 , including housing 102 and door 103 , may be positioned at a region 17 under the register belt 14 for ease of access and usage by a store associate behind the checkout counter. The door 103 of the system 100 may be used in lieu of a door of the counter compartment 17 .
[0041] In doing so, the door 103 may be constructed and arranged to match the register belt counter 16 , for example, same color, texture, material, alignment, quality, and/or shape for insertion into the counter compartment 17 , and so on. The garbage bins 112 , 113 may move in a linear direction in and out of a compartment 17 in a region of the counter 16 under the register belt 14 due to sliding rails 104 or the like, which extend and retract when a user pulls or pushes one or both garbage bins 112 , 113 when needed. An outermost edge of the housing, the door 103 , or the bins themselves may be flush with a surface of the register belt area or other regions of the counter so as to not protrude from the counter, and therefore provide a compact configuration when closed. However, when at least partially opened, for example, rails extended to expose some or all of the bins 112 , 113 , some protrusion may occur. The counter 16 may include a door (not shown) in an opened position when the sliding rails 104 are in an extended position, and the garbage bins 112 , 113 are therefore outside of the compartment 305 . The door may be in a closed position when the sliding rails 104 are in a retracted position, and the garbage bins 112 , 113 are inside the compartment 305 .
[0042] In some embodiments, the retail store checkout counter serves as a hybrid register, for sorting garbage from recyclables such as hangers, plastic bags etc. at the checkout counter. The garbage collection system 100 can be constructed and arranged for one or more of garbage collection, recyclable collection, hangers' collection, returns collection (for example, bottles, cans, and so on), or anything else having a size and configuration for insertion into one or both bins 112 , 113 .
[0043] While concepts have been shown and described with reference to specific preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the following claims.
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A garbage collection system comprises a housing positioned under a belt of a point of sale register counter; first and second bins positioned in the housing under the point of sale register counter, the first bin for receiving garbage and/or recyclables, the second bin for receiving hangers; and at least one sliding rail extending perpendicular from a height of the housing, the first and second bins coupled to the at least one sliding rail, at least one of the first and second bins retracting or protruding from at least a portion of the housing in a first position and positioned entirely in the housing in a second position.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to U.S. patent application Ser. No. 12/823,652, filed on Jun. 25, 2010, entitled, “System, method and device for solving problems in NP without hyper-polynomial cost,” now U.S. Pat. No. 8,577,825 B2, which is hereby incorporated by reference herein.
BACKGROUND
[0002] Computational complexity theory is a branch of computer science that focuses on classifying computational problems according to their inherent difficulty. One such classification is “NP”, which is the class of problems that can be solved in polynomial time by an algorithm running on a non-deterministic Turing machine. An algorithm is said to run in polynomial time if its running time is upper-bounded by a polynomial function of the size of the input for the algorithm, i.e., T(n)εO(n k ) for some constant k. The present invention might be compared to the Newton Method, the Davis-Putnam-Logemann-Loveland (DPLL) algorithm, and the Conflict-Driven Clause Learning (CDCL) algorithm.
SUMMARY
[0003] Embodiments of the present invention address problems associated with automated solution of NP, NP-complete, and NP-hard problems in polynomial time without the need for tuning. Embodiments of the present invention may be implemented using any of a variety of techniques, such as computer-implemented methods and/or systems. Any reference herein to embodiments of the present invention which are implemented using a “method” or “methods” should be understood to include embodiments implemented using methods and/or systems. Similarly, any reference herein to embodiments of the present invention which are implemented using a “system” or “systems” should be understood to include embodiments implemented using methods and/or systems.
[0004] Embodiments of the present invention provide a method for solving NP, NP-complete, or NP-hard problems in polynomial time without the need for tuning. Certain embodiments of the present invention include a method which includes converting a given problem definition into an expression composed of one or more constraints; selecting assumed value predicates for the variables of the expression; propagating the implications of the assumptions; identifying any contradictions caused by the implications of the assumptions; determining, for each identified contradiction, whether that contradiction can be moved towards a corresponding location where it will resolve as an implication; for each contradiction which can be so moved, moving that contradiction towards its corresponding location; and, for any contradiction which cannot be so moved, reporting that the expression is unsatisfiable.
[0005] Embodiments of the present invention provide a method for improving the time requirement of solving of a logical or numerical problem by resolving conditional contradictions arising during the solving of the problem, without the need for tuning. The problem is formed of constraints, each of which includes one or more variables. Solving the problem includes determining whether the problem is satisfiable by a set of variable values or unsatisfiable when there are no sets of variable values that satisfy the expression. The problem may be a logical expression in conjunct normal form (CNF) such that it is a conjunction of a set of constraints, where each of the constraints is a disjunction of several variables. The method includes receiving, as part of the problem being input to a computer, unconditional assertions regarding values of zero or more of the variables; making assumptions regarding values of one or more of the variables that are not subject of the unconditional assertions; and using the assumptions or the unconditional assertions to make assertions of terms regarding values for other variables of the problem. A constraint is forced to assert a term when, as a result of existing assumptions or assertions, the values of all but one of the terms are restricted. Then, for the constraint to be satisfied, the one remaining term becomes asserted and cannot be negated without creating a contradiction. If the value of the asserted term is not already determined, it becomes determined. At this point, the constraint is asserting, and if it caused the value of the asserted term to become determined, then the assertion and the constraint that asserts it becomes prevailing. The method continues with setting values for the variables as determined values responsive to the unconditional assertions, the assumptions, or the generated conditional assertions. The variables not having a determined value are called free variables. The iteration of the making of assumptions, the making of assertions, and the setting of values for the variables as determined, forms the process of implication. A contradiction may be conditioned on the assumptions and arises when all terms of some constraint are restricted. The method moves a contradiction by forcing the assertion of a value of a term of a first contradicted constraint which in turn restricts terms of the same variable in other constraints that are not already restricted or negates disagreeing asserted values or assumptions of the same variable, possibly producing a contradiction in a contiguous second constraint and always resolving the contradiction in the first constraint. The method directs this motion of the contradiction in order to expel the contradiction from the problem. It is advantageous for the method not to force the assertion of a value of any term that is unconditionally negated. It is also advantageous for the direction of motion of a contradiction to be chosen in such a way that all possible paths of escape will be explored if the contradiction cannot be expelled. The method detects when the term being counter-asserted has no assumptions in the path behind the direction of motion and marks that assertion as being unconditional. The method continues by reporting that the problem is satisfied if the count of the free variables is zero and all contradictions have been expelled, or by reporting that the problem is unsatisfiable if a contradiction is encountered where all the terms are unconditionally negated.
[0006] The technical consequence of such embodiments is comparable to the invention of random access memory (RAM) because RAM provides an improvement in data access times that is logarithmic compared to previous linear time requirements, and such a ratio is similar to the ratio between polynomial time and hyper-polynomial time. Without RAM many current products would be impossible, and similarly many new products will become possible with the introduction of embodiments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows a Variable and Constraint diagram that demonstrates by example that a process that parameterizes teardrops as summarizing constraints, as DPLL and CDCL do, is insufficient to avoid hyper-polynomial computational costs without some form of tuning.
[0008] FIG. 2 shows a flowchart of a method performed by a computer system implemented according to one embodiment of the present invention.
[0009] Referring to FIG. 1 , in a Variable and Constraint diagram, the white circles represent variables and the lines represent constraints. A term is represented by a constraint line traversing a variable circle. Lines that traverse a variable circle in a vertical way represent terms that have the ‘0’ value predicate for that variable. Lines that traverse a variable circle in a horizontal way represent terms that have the ‘X’ value predicate for that variable. The variable circles are labeled with a letter of the Latin alphabet. The expression represented in FIG. 1 is identical to the expression represented in the following table:
[0000]
B
CDEF
GHJK
MNPQ
RSTU
Z
1
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2
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3
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X
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X
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4
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X
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5
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X
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6
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X
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7
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X
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8
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X
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9
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X
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10
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X
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X
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11
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X
X
X
X
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12
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13
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14
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X
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15
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X
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X
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16
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17
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X
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X
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18
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19
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20
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X
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21
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X
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22
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23
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24
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X
[0010] The left-hand side of the table numerically labels the constraints that are unlabeled in the diagram, and the top of the table reiterates the labels of variables that appear in the diagram.
[0011] When xB is assumed, the following assertions are forced: oT, oU.
[0012] When xC, xD, xE, and xF are then assumed, no subsequent assertions follow.
[0013] When xG is then assumed, the following assertions are forced: xR, xS, oP, oQ, xM, xN, and either oZ or xZ. At this point, a contradiction exists in the logical expression. We will presume that the contradiction exists in constraint 23.
[0014] We now describe the behavior of an algorithm that parameterizes teardrops as summarizing constraints using stratified reasons:
[0015] The contradiction in constraint 23 has three assumptions in its reason, xB, xC, and xG. Because stratified reasons are being used, the precipitant of this teardrop must be in a path that contains xG. The identified precipitant in this case is xG itself. The summarizing constraint produced is a disjunct phrase containing the following terms: oB, oC, oG.
[0016] The consequence of removing the most recent assumption and the assertions it entails is that oG is asserted and no subsequent assertions follow.
[0017] When xH is then assumed, the following assertions are forced: xR, xS, oP, oQ, xM, xN, and either oZ or xZ. At this point a contradiction exists in either constraint 23 or 24 that has three assumptions in its reason, xB, xC, and xH. Because stratified reasons are being used, the precipitant of this teardrop must be in a path that contains xH. The identified precipitant in this case is xH itself. The summarizing constraint produced is a disjunct phrase containing the following terms: oB, oC, oH.
[0018] The consequence of removing the most recent assumption and the assertions it entails is that oH is asserted and no subsequent assertions follow.
[0019] When xJ is then assumed, the following assertions are forced: xR, xS, oP, oQ, xM, xN, and either oZ or xZ. At this point a contradiction exists in either constraint 23 or 24 that has three assumptions in its reason, xB, xC, and xJ. Because stratified reasons are being used, the precipitant of this teardrop must be in a path that contains xJ. The identified precipitant in this case is xJ itself. The summarizing constraint produced is a disjunct phrase containing the following terms: oB, oC, oJ.
[0020] The consequence of removing the most recent assumption and the assertions it entails is that oJ is asserted and this forces the following assertions: xK, xR, xS, oP, oQ, xM, xN, and either oZ or xZ. At this point a contradiction exists in either constraint 23 or 24 that has two assumptions in its reason, xB and xC. Because stratified reasons are being used, the precipitant of this teardrop must be in a path that contains xC. The identified precipitant in this case is xC itself. The summarizing constraint produced is a disjunct phrase containing the following terms: oB, oC.
[0021] The consequence of removing the most recent assumption and the assertions it entails is that oC is asserted and no subsequent assertions follow.
[0022] Following the pattern that is now established, the following summarizing constraints are produced: (oB, oD, oG), (oB, oD, oH), (oB, oD, oJ), (oB, oD), (oB, oE, oG), (oB, oE, oH), (oB, oE, oJ), (oB, oE), (oB, oG), (oB, oH), (oB, oJ), (oB). Further assumptions of C, D, E, F, G, H, J, and K do not produce any contradictions.
[0023] The variables C, D, E, and F have identical connections to other variables, and the same can be said for the variables G, H, J, and K. We can interpret the variables C, D, E, F, M, N, P, and Q as a block of variables and constraints that have internal connections that are congruent with the internal connections of G, H, J, K, R, S, T, and U, another such block; and we can interpret the cardinality of the sets {C, D, E, F} and {G, H, J, K} as the “size” of these blocks. These blocks are connected in series with an initial segment consisting of the constraints that contain terms of B, and a terminal segment consisting of constraints that contain terms of Z.
[0024] The number of summarizing constraints produced by this example is equal to the product of the sizes of the blocks. If the number of variables in the identically connected sets is varied, then the number of summarizing constraints produced continues to be the product of the sizes, as long as the block adjacent to the initial segment does not have its size reduced to 1. If additional blocks are inserted into the series, the number of summarizing constraints produced will be the product of the sizes of all the blocks, as long as B remains the variable of the first assumption, and as long as the block adjacent to the initial segment is always the last block in which assumptions are made. A product of block sizes is a hyper-polynomial number, and therefore the method used in the description above does not provide a solution without hyper-polynomial cost.
[0025] Given the same assumptions, regardless of order, embodiments of the present invention, which does not parameterize teardrops as summarizing constraints, will come to the conclusion that oB is unconditionally asserted with a single counter-reversal through Z rather than a number of traversals through Z that is the product of the sizes of the blocks. It is possible to construe, with some difficulty, that the example algorithm that produces summarizing constraints moves contradictions through a proximal space, but the transitions move contradictions from one teardrop directly to another, and each teardrop is such that if we also construe the assertion that results when the latest assumption is removed to be a counter-assertion, then it is always the case that such a counter-assertion no longer has the latest assumption in its reason. On the other hand, because embodiments of the present invention move contradictions contiguously through the same proximal space, they are able to detect relationships that the example algorithm misses or detects only after great effort, and this detection occurs specifically when the contradiction reverses through a point of former divergence which is not a precipitant such that the latest assumption is removed from the reason of the counter-assertion, or when a contradiction causes an assumption to be negated and counter-assertion or implication continues outside a single stratum.
[0026] There are embellishments to the discussed algorithm that produce summarizing constraints which may avoid a hyper-polynomial cost. One such embellishment is to apply assumptions to the initial segment and then to the blocks in order of their nearness to the initial segment. Such an embellishment requires prior analysis of the overall structure of an expression in order to decide, for example, which value predicates should become assumptions, and embellishments that require prior analysis are effectively tuning the algorithm to the specific structure of the expression. Other embellishments often do not work in all cases without prior analysis of the structure of an expression, which is why the Clay Mathematics Millennium Prize for this problem has not been awarded previously. Embodiments of the present invention include improvements that work in all cases without prior analysis of the structure of the expression.
DETAILED DESCRIPTION OF THE INVENTION
[0027] Embodiments of the present invention provide systems, methods, and/or devices for improving the performance of machines that solve problems in the complexity classes called “NP,” “NP-complete,” and “NP-hard”.
[0028] “P” is a class of problems that can be solved by a deterministic Turing machine in polynomial time. A deterministic Turing machine engages in serial or limited parallel-processing. “NP” is a class of problems that can be solved by a non-deterministic Turing machine in polynomial time. A non-deterministic Turing machine is capable of unlimited parallel-processing. “NP-complete” is a subset of hard problems in NP whose membership in P is doubted. Examples of NP-complete problems are the Traveling Salesman Problem and the Satisfiability or satisfaction (SAT) Problem. NP-complete problems pertain to a number of technical fields. “NP-hard” problems are those problems which have a component that is known to be NP-complete but which have other components and those other components are tractable but otherwise are unclassified.
[0029] The conjunct normal form represents an expression as a list of conjunct (“ANDed”) constraints where each constraint is composed of one or more disjunct (“ORed”) logical terms. A “term” is a particular instance of a value assignment (usually “true” or “false”) for a particular variable where the particular value assignment occurs in the context of a particular constraint. Therefore, a term is a value of a variable in the context of a particular constraint. The same value of the same variable in a different constraint represents a different term. It is known that the representation of any problem which is in NP has a conversion to a logical expression in conjunct normal form which does not incur a hyper-polynomial cost.
[0030] Computationally, space and time are polynomially exchangeable, so we talk generally about polynomial cost rather than specifically about polynomial time. Being able to determine the satisfiability of arbitrary conjunct normal form expressions in polynomial time with a deterministic machine is therefore equivalent to being able to solve any NP-complete or simpler problem without hyper-polynomial cost.
[0031] Prior to the present invention, solutions to NP-complete problems, as well as many other problems in NP, such as Integer Factoring, have either required an exhaustive search of possible value assignments for the variables represented in the problem, or otherwise required hyper-polynomial costs, such as N! or 3 N , rather than polynomial costs such as N 3 , where N is the size of the input to the problem. Embodiments of the present invention, in contrast, may find solutions to NP-complete problems, and other problems in NP, without requiring an exhaustive search of possible value assignments for the variables represented in the problem, and without otherwise requiring hyper-polynomial costs. Just as a multiplication circuit in a conventional computer permits the product of 255 and 37 to be computed in a number of elementary steps that is proportional to the number of bits in its registers (shift the result for each “zero” bit and add the first argument for each “one” bit in the second argument) rather than a number that is proportional to the value of the second argument (iterative add), which is a logarithmic reduction in computational cost, embodiments of the present invention permit a computer, whether conventional or purpose-built, to solve NP-complete problems or other problems in NP in a number of elementary steps that is less than a number that is proportional to the fifth exponent of the number of variables in the problem rather than a number that is hyper-polynomial. Embodiments of the present invention thereby enable a reduction in computational cost that is comparable to the reduction from linear to logarithmic cost.
[0032] One reason that computers were invented was to reliably and quickly solve difficult problems. Embodiments of the present invention, which may be implemented as computer processors and/or computers, provide a very significant improvement to automatic computing devices as well as to other machines that use computers to control their behavior. This improvement greatly reduces the amount of power, cooling, rent, and other costs that are required in order to establish and operate a computer while decisions are being computed, as well as reducing the time that operators of the computer must wait for a result. An automatic computing device that is augmented with embodiments of the present invention may no longer require to be programmed in a conventional way; instead, such a device or system accepts the set of constraints as the requirements to be met, whether those are structural or behavioral requirements, and the machine outputs a result or operates in a manner that satisfies those constraints.
[0033] One means by which embodiments of the present invention may deliver their improvements to the performance of computers and other devices that perform automated processes is by imposing a specific arrangement of switches within the computer and these switches rely on the physical property of exclusion. Exclusion among fermions is inherent in that no two fermions, or particles, of the same type can occupy the same space at the same time; so forcing one particle into position may force another particle out of position, as when the teeth of one gear push against the teeth of another gear that is meshed with the first, thus switching the positions of both gears while only applying external force to one. Exclusion among bosons is inherent in the potentials we can engineer across carriers—we arrange that the potential is always either high or low, as in a transistor. Because many kinds of switches that operate on a variety of substrates are well-known, and the improvement provided by embodiments of the present invention is inherent in the arrangement of switches rather than the type of switch or substrate, language peculiar to specific kinds of switches is not used in the description of the present invention, and language that seems abstract, such as discussion of sets, orderings, or networks, is used because the language is precisely descriptive of the desired behavior for the arrangement of switches that is an embodiment of the present invention. This use of language is similar to how we may describe the structure of a gear, perhaps specifying the relative stiffness of the material out of which it is made rather than specifying whether it is made of wood or metal and without describing the carving or casting that might be used to produce the gear, because it is well known by practitioners of those arts how to produce the described object. This use of language is also similar to how we may describe a clockwork mechanism that is constructed out of a set of ready-made gears and springs in the vocabulary of rotational ratios and syncopation, without describing the details for constructing each of the ready-made parts, because we know that such parts are available, and how to mount those parts in order to produce the described effect is well-known to practitioners of the art. Yet none of this use of language obviates the fact that embodiments of the present invention may be implemented as machines and as methods that control machines, no matter how abstract the language that may be used to describe such machines and methods.
[0034] One embodiment of the present invention is a data processing system which solves given NP, NP-complete, or NP-hard problems using a deterministic machine in polynomial time. The given problem definition is converted into an expression composed of logical or otherwise deterministic constraints. Next, a process of assuming values for the constraint variables as-needed, tracking the paths of implications resulting from value assumptions, choosing one path for each value implicated, resolving any contradiction of a constraint by choosing a contradiction-causing value to be negated by using the path tracking to inform the decision, always negating a value asserted by a path that contains an assumption or pseudo-assumption, and then converting the contradicted constraint into an asserting constraint, is iteratively applied to the expression until either no contradicted constraints remain and every variable obtains a value, or else a contradicted constraint exists for which there is no value to be negated that is asserted by a path that contains an assumption or a pseudo-assumption. The number of iterations of each portion of this process is bounded by a polynomial of the size of the expression.
[0035] Embodiments of the present invention may be implemented as one or more devices and/or automated processes that process information in order to render decisions efficiently. The behavior of such embodiments may be explained using a system of objects, necessary relationships that contribute to the definition of what those objects are, and transformations that alter the states of those objects in ways that are consistent with the necessary relationships. Certain vocabulary used to describe embodiments of the present invention are described below.
[0036] Sets
[0037] The disclosure herein uses the mathematical language of “sets”. Well-known operations that combine sets are “union” and “intersection”. Well-known comparative operations between sets are “subset” and “superset”. For clarity, “subset” and “superset” include the possibility that the two sets being compared are identical, whereas “proper subset” and “proper superset” exclude that possibility. The well-known concept of a “mapping” between sets is also briefly mentioned, as is a class of “set relation”.
[0038] Variables
[0039] Each “variable” is a locale of variability, which can be characterized as a set of values. For example, each variable is the name of a logical predicate which appears in the given expression. In application, a variable could be the set of valid voltages supplied to a pin on a computer chip, a numeric register, an alphanumeric string in some programming language, or any data structure that has the property of representing one (or no) value at a time and can represent more than one value over time. In this respect, a variable here is similar to a variable in the domain of software engineering.
[0040] Values
[0041] The “values” of a variable, as used herein, are practically enumerable or practically delimitable. Problems that contain variable values that are not practically enumerable or delimitable might not be in NP. By definition, the values of Boolean variables are practically enumerable.
[0042] “Atomic values” are the indivisible mutually exclusive cardinal values of a variable. For a numeric variable X, “3” would be an atomic value, and “{ 2 , 3 }” and “X<3” would not be atomic values.
[0043] Note that a variable could be defined as a logical predicate on a numeric variable that does not otherwise appear in the expression. In this case, the expression variable is Boolean not numeric, and the atomic values of the expression variable are “true” and “false”, not numbers.
[0044] Value Predicates
[0045] “Value predicates” are statements that define a specific subset of atomic values of a variable. A set containing all atomic values of a variable is not a valid value predicate. A set containing no atomic values is not a valid value predicate. In other words, “null” and “inherent contradiction” are not valid values in the way of speaking used herein. For example, “X=3”, “X>3”, “2<X<3”, “X modulo 2=1”, “Xε{2,3}”, and “X=complement(2<N<3)” (when N does not refer to a variable of the expression, as defined here, but to a para-variable strictly used to independently define a value predicate) are all valid value predicates for a numeric variable, while “X=Y”, “1<X<0”, and “X=complement(1<N<0)” are not valid value predicates.
[0046] When we write about a conjunction of predicates, this is identical to an intersection of the sets of atomic values represented by the predicates.
[0047] In all cases where we describe behavior in the vocabulary of values of variables, we are describing the behavior of switches. We may interpret a switch state or the states of an ordered or unordered collection of switches as a “number”, a “Boolean value”, or a “predicate”, and this is often the engineering intent, but it is merely a descriptive convenience—the behavior that is described is the behavior of switches and not of numbers, sets, or logical states per se.
[0048] Terms
[0049] A “term” is primarily composed of a reference to, or a reproduction of, a variable within the context of a constraint. An explanation of “constraint” is provided farther below.
[0050] Certain embodiments of the present invention may be embedded in a system that is interpreted as using two-valued logic. In two-valued logic, a term is typically interpreted as representing a Boolean value of the variable. This is a short-hand for a claim that the term effectively represents a value of the term's variable that is interpreted to be either “true” or “false” for logical models, or either “1” or “0” for digital numeric models, or “high-voltage” or “low-voltage” for transistor circuits, or even as (for example) either “hug” or “kiss” for a thoroughly abstract model. The imperative for two-valued logic is that there is no third value and, therefore, in order that there be a problem to solve, the two values must disagree, regardless of what names we give to the values. We call such a term a Boolean value predicate.
[0051] Certain embodiments of the present invention may be embedded in a system that is interpreted as using many-valued logic. An example of a many-valued logic is first-order logic, which includes representations of numbers. In many-valued logics, a term may represent a Boolean value as in two-valued logic, but it may instead represent a value of some variable that is not the subject of an explicit predicate. When representing a value of such a variable, we call such a term a non-Boolean value.
[0052] Instead of representing any specific set of values, a term in a many-valued logic may be part of an equality or inequality relationship with other variables. In order for a term to be part of an equality or inequality relationship with other variables, the relationship must meet special requirements. An explanation of these special requirements is provided in the discussion of SOMMEs below.
[0053] Regardless of whether an embodiment is interpreted as using two-valued logic or many-valued logic, there may be many terms in the expression, each referencing the same or different variables.
[0054] Phrases
[0055] A “phrase” contains an addressable set of terms representing value predicates. A phrase contains any number of terms, but for each term in the phrase, there may be no other term that represents a value predicate of the same variable. Each phrase also represents either a conjunction or disjunction of the value predicates it contains. A numerically represented vector is an example of a conjunct phrase, and a CNF constraint is an example of a disjunct phrase.
[0056] Constraints
[0057] In two-valued logic, a “constraint” is represented by a non-empty disjunct phrase of Boolean terms. In multi-valued logics, a constraint may be represented by either a disjunct phrase or a satisfiable-or-mutually-mapped expression (SOMME).
[0058] SOMMEs
[0059] A “SOMME” is a sub-expression which represents a relationship among variables such that determining the values of all but one of the variables in the sub-expression either satisfies the sub-expression or else implies the truth of a value predicate for the one variable which was not previously determined, regardless of which variable is the one not previously determined, and regardless of the specific determined values. For example, if R is the set of real numbers, and x, y, zεR, then “x+y=z” is a SOMME, but “x*y=z” is not because if, for example, x=0 and z=0 the value of y could be any number and remains unknown. However, “x=0 OR y=0 OR x*y=z” is a SOMME because it removes the possibility of one of the factors being 0 unless the entire statement is satisfied. Similarly, “x 3 =y” is a SOMME, and “x<0 OR y<0 OR x 2 =y” is also a SOMME, but “x 2 =y” is debatable.
[0060] In the case of “x 2 =y”, when y is determined to be a single atomic value in the Real numbers, x could be either the positive square root of y or the negative square root of y. If we accept only atomic values as implied values, then “x 2 =y” is not a SOMME, but if we permit sets to be implied values then “x 2 =y” is a SOMME. What values are allowed to be implied is a decision that may be inherent in the definition of the problem to be solved; so after this point, the terminology used is that “value predicates” are implied, and this terminology permits either interpretation of what constitutes a SOMME.
[0061] In the case of “x=0 OR y=0 OR x*y=z”, if a determinant for y exists so that y=1, and then a determinant for x is introduced so that x=0, there is no assertion for z because the first part of “x=0 OR y=0 OR x*y=z”, i.e. “x=0”, is not restricted. This is what is meant by “satisfying the sub-expression”.
[0062] Disagreement
[0063] Value predicates of the same variable which have an empty set of atomic values in their intersection are said to “disagree”.
[0064] Complementariness
[0065] One set of value predicates is “complementary” to another set of value predicates for the same variable if no predicate in either set disagrees with the other predicates in the same set, the intersection of the first set disagrees with the intersection of the second set, and every atomic value of the variable is in either one set or the other exclusively. In two-valued logic, each variable value is complementary to the only other possible value for that variable and disagrees with it.
[0066] Uncontroversiality
[0067] If, for one variable, the conjunction of all the value predicates represented in all the constraints do not disagree, and there are no SOMMEs that have terms of that variable, then the variable of those terms is said to be “uncontroversial”.
[0068] Determinants
[0069] When a conjunction of value predicates is considered to be true, whether provisionally (a.k.a. “conditionally”) or necessarily (a.k.a. “unconditionally”), we call the set of atomic values that result from the conjunction a “determinant”.
[0070] Restriction
[0071] We say that a determinant restricts the value of a term in a disjunct phrase if the determinant disagrees with the term.
[0072] We say that a determinant restricts the value of a term in a SOMME if the SOMME has a term of the same variable and any of the following three cases applies:
not all terms in the SOMME represent variables that have determinants, and this determinant does not satisfy the SOMME; or as a consequence of this determinant, the SOMME implies a non-tautological value predicate for a variable other than the variable represented by this term; or all terms in the SOMME represent variables that have determinants, and if the given determinant did not exist, the SOMME would imply a value predicate for the variable represented by the term of the same variable as the given determinant, but that value predicate would disagree with the given determinant.
[0076] Assertions
[0077] When determinants restrict all but one of the terms in a constraint, a value predicate is “asserted” for the variable of the one unrestricted term. If all the restricted terms of a constraint are unconditionally restricted, then an assertion of that constraint imposed by those restrictions is trivially unconditional. Also, if a constraint contains only one term, the value predicate represented for that term is trivially unconditionally asserted. Otherwise, if any of the terms of a constraint is not unconditionally restricted, but the constraint asserts a value predicate, that assertion is conditional. When some constraints contain terms that represent value predicates that represent sets of atomic values with more than one member, it is possible for a constraint to unconditionally assert a first value predicate and to conditionally assert a second value predicate that is a proper subset of its unconditional assertion.
[0078] A constraint may continue to have a conditional assertion even after one or more of its conditional restrictions are removed. Unconditional restrictions cannot be removed.
[0079] Restriction Support
[0080] Extant assertions that represent the same variable are said to “conjunctively converge”, and the intersection of the value predicates represented by the extant assertions is the extant determinant for that variable. If a given class of extant assertions conjunctively converge to produce a determinant that represents a set of atomic values that is a subset of the restriction on a term, then the given class of assertions is said to “fully support” that restriction.
[0081] Prevalence
[0082] Conjunctions of assertions (a.k.a. intersections of sets of atomic values represented by the value predicates that are asserted) become the determinants for their common variable.
[0083] Many constraints may assert a single atomic value or another value predicate that represents a set of multiple atomic values for the same variable. When the constraints of an expression do not contain value predicates that represent sets of atomic values with more than one member for the same variable, such as when two-valued logic applies, then at most one of the assertions of that same variable is “prevailing”. Otherwise, it is possible to have multiple prevailing assertions for the same variable.
[0084] Usually the assertions in the conjunction that composes a determinant are prevailing assertions. In the case of unconditional assertions, the assertions are usually prevailing. Among prevailing unconditional assertions for the same variable, the intersection of sets of atomic values represented by the value predicates of those assertions becomes the unconditional determinant. Among conjunct conditional assertions for the same variable, the intersection of the sets of atomic values represented by the value predicates of those assertions and the prevailing unconditional assertions becomes the conditional determinant. The determinants are updated each time an assertion is added to the conjunction. Assertions are usually added to the conjunction when they become prevailing.
[0085] When only one prevailing assertion is allowed for each variable, any unconditional assertion for that variable is the one that prevails. When only one prevailing assertion is allowed for a variable, and there are no unconditional assertions for that variable and there are multiple conditional assertions that could be prevailing, then the choice of which assertion to designate as prevailing is arbitrary and is most easily rendered by taking the first such assertion that presents itself. (See farther below for a discussion of conditional assertions that cannot become prevailing regardless of what other assertions exist.)
[0086] When more than one prevailing assertion is allowed for each variable, then the assertions should be segregated according to their conditionality, as described below.
[0087] Among unconditional assertions that are candidates for being designated as prevailing, the first such assertion that presents itself should be made prevailing. If a subsequently presented unconditional assertion for the same variable represents a proper subset of the atomic values contained in any value predicates represented by previously presented prevailing unconditional assertions, then those previously presented assertions usually become non-prevailing and the subsequently presented assertion always becomes prevailing. If a subsequently presented unconditional assertion does not represent a subset of any of the previously presented prevailing unconditional assertions, and the intersection of the subsequently presented unconditional assertion with the intersection of the previously presented prevailing unconditional assertions is a proper subset of the intersection of the previously presented prevailing unconditional assertions, then the subsequently presented assertion becomes prevailing. In all other cases, a subsequently presented unconditional assertion usually does not become prevailing. It is acceptable, though less efficient in many cases but more efficient in a few cases, to ignore these rules and make all unconditional assertions prevailing.
[0088] If a subsequently presented unconditional assertion represents a value predicate that is a subset of the value predicate for a previously presented prevailing conditional assertion for the same variable, then the previously presented conditional assertion may (but need not) become non-prevailing. Similarly, in cases above where unconditional assertions usually become non-prevailing but in fact remain prevailing, the efficiency of the present invention is reduced but not to the point that it becomes hyper-polynomial. The discussions below presume that such assertions become non-prevailing.
[0089] Among conditional assertions that are valid candidates for being designated as prevailing when no unconditional assertions for the same variable exist, the first such assertion that presents itself should be made prevailing. If the intersection of the set of value predicates represented by a subsequently presented valid candidate conditional assertion and the intersection of the previously presented prevailing unconditional and conditional assertions for the same variable is a proper subset of the intersection of the previously presented prevailing unconditional and conditional assertions, then the subsequently presented assertion becomes prevailing. In all other cases, a subsequently presented conditional assertion does not become prevailing. (Invalid candidates for being designated as prevailing are discussed farther below.)
[0090] As each assertion becomes prevailing, it may be associated with the next number in a sequence. This number is called the “prevalence” number of the assertion.
[0091] Assumptions
[0092] During processing, we may create one or more assertions that are not produced by constraints and which are for a variable that previously had no determinant, or has a determinant but the determinant represents a set containing more than one atomic value. Such an assertion is called an “assumption” or an “assumptive assertion” and its value predicate is “assumptive”. In contrast, assertions that are forced from constraints are called “implicated assertions”. Assumptions are always conditional, and each value predicate must contribute to the determinant for the variable the assumptive value predicate represents.
[0093] In some embodiments of the present invention, it is possible to make assumptions implicitly rather than explicitly. For example, if constraints are organized into groups, where each member of a group has some terms that represent value predicates that are in a certain set of value predicates that identifies that group, and this organization exists in order to compare the productive interaction of other terms in the same constraints that represent value predicates or variables that are not in this certain set, then the organization of constraints effectively assumes common restrictions on the terms in each set of common value predicates.
[0094] Contradictions
[0095] When all the terms of a constraint are restricted, there is a “contradiction” in the constraint. An expression is unsatisfiable if it contains any constraint that has all of its terms unconditionally restricted.
[0096] Satisfaction
[0097] Any constraint is “satisfied” when one or more of its terms is not restricted and the variable of that term has a determinant. An expression is satisfied when none of its constraints are contradicted and all variables have determinants that represent a set containing a single atomic value.
[0098] In cases where sets of atomic values are acceptable as value predicates, it is possible that the expression may be satisfied when all constraints are satisfied and all variables have determinants, not requiring that each determinant represent a set containing a single atomic value, but whether this is the case or not depends on the specific qualities of the expression. Generally, if an expression contains any mapping of two sets that is a reordering of another direct or indirect mapping of the same two sets, then the expression should be treated as requiring single-value predicates for expression satisfaction.
[0099] Pools
[0100] A “pool” is an addressable set to which elements can be added and removed. As a pool per se, elements may be added to or removed from the pool in any order. Pools may also incorporate specific rules for the order in which added elements are removed. For example, non-prioritized queues incorporate a “first-in-first-out” (FIFO) rule, and stacks incorporate a “first-in-last-out” (FILO) rule.
[0101] Both stacks and queues are specific kinds of pools. Stacks have elements “pushed” down onto them and “popped” off of them. In the case of queues, elements are “enqueued” and “dequeued”. Initially, all pools are empty, and when the last element has been popped off a stack or dequeued from a queue, the pool is again empty.
[0102] Implication
[0103] “Implication” is a process that is triggered when a new determinant is introduced. In this process, the terms that are restricted by the new determinant are identified, and then the constraints of those terms are checked to see if all or all but one of the terms in each constraint is restricted.
[0104] If a constraint is not satisfied and all but one of the terms in the constraint are restricted, then the constraint asserts a value predicate. New assertions may or may not become prevailing, as described above. If a new assertion becomes prevailing, then a new determinant is introduced and these steps are repeated. Because many assertions may be produced from the introduction of a single determinant, it is necessary for an implication process either to have a pool to manage the assertions and resultant determinants or to have a mechanism that provides parallel paths of operation.
[0105] Implication may halt as soon as a constraint becomes contradicted and always halts when no new prevailing assertions were produced in the most recent iteration of the implication process.
[0106] For efficiency, whenever a first unconditional determinant is introduced to the expression, any other unconditional assertions that may be forced by the first unconditional determinant should be propagated through the expression before any further conditional implication or other action that may introduce another conditional determinant occurs.
[0107] Proximity in Rhizomatic Networks
[0108] The propagation of implication is founded on the notion of restriction, which can only be productively conveyed between any two constraints where each constraint contains terms that represent value predicates for the same variables as are represented by terms in the other constraint, and among these terms exactly one term restricts the term that represents the same variable in the other constraint. In two-valued logic, this means that exactly one term represents a value predicate that disagrees with the value predicate of the matching term in the other constraint, and all other predicates either have no matching terms that represent the same variable or else the other predicates represent the same value predicate as is represented by its matching term.
[0109] In the case of the mutually-mapped portions of SOMMEs, the same relationship is necessary in order to be productive (i.e., a single term in one constraint may restrict a single term in another constraint), but this fact is usually obscured by a presumption that no SOMME in an expression represents a subset of the mapping represented by another SOMME in the expression. When this presumption is correct, all SOMMEs that are not satisfied that have terms that share common variables have a productive relationship, but it is the singular nature of the restriction that makes the relationship productive, not the singular or multiple nature of the commonality of variable.
[0110] The structure that is made apparent by the collective implicational exercise of these pair-wise productive relationships provides two forms of convergence. Two assertions may converge conjunctively by representing non-disagreeing value predicates for the same variable. Two assertions may converge disjunctively by restricting different terms in any single constraint which then asserts some other value predicate. Among assertions that conjunctively converge, assertions that are not subsets of other assertions are usually made prevailing. Among assertions that disjunctively converge, all are prevailing before they converge.
[0111] Because the implicational structure is produced by two different forms of conjunction, it would be imprecise, though not incorrect, to call the structure partially ordered, a collection of lattices, or a conventional network. Instead, we call the implicational structure a “rhizomatic network” in order to emphasize that operations that have been defined to work on conventional networks may be analogous to operations that are defined to work on rhizomatic networks, but the mechanical specifics and increased number of functional cases that must be handled by some operations of the present invention that work on rhizomatic networks make these operations significantly different from the analogous operations that have been defined to work on partially ordered sets or conventional networks.
[0112] Two constraints that have a productive relationship, as described above, and for which the assertion of one constraint actually restricts a term in the other constraint are said to be “contiguous” in the implicationally apparent rhizomatic network. Proximity, as the word is used here, is founded on distance across the contiguous constraints in an implicationally apparent rhizomatic network, and the space defined by extended contiguity is a proximal space.
[0113] Handling Contradictions & Assumptions
[0114] Some method of direct reference between terms and variables and constraints should be implemented. In software, this is normally accomplished by creating indexes. In electronic hardware, this may, for example, be accomplished with wiring.
[0115] Constraints that contain terms that represent uncontroversial variables can be safely removed.
[0116] Any constraint that contains only one term constitutes an unconditional assertion of the value predicate represented by the term. Whenever a new unconditional assertion is recognized, implication should occur.
[0117] If implication has halted and there are no contradicted constraints, then an assumption should be created for a variable that has no determinants, or if all variables have determinants, an assumption should be created for a variable that has a determinant that represents a set containing more than one atomic value which reduces the cardinality of the set represented by the determinant, and then implication should occur.
[0118] If implication has halted and there are one or more contradicted constraints, then one contradiction should be resolved in some fashion, and then implication should occur. This step should be repeated until either there are no more contradicted constraints or an unconditional contradiction exists.
[0119] All the above steps should be repeated until a necessary contradiction exists, in which case the expression is unsatisfiable, or else until the expression is satisfied.
[0120] Resolving a Contradiction
[0121] If all of the terms in a constraint are restricted, a contradiction exists in the constraint. If all the terms of a contradicted constraint are unconditionally restricted, then a necessary contradiction exists, and the expression is unsatisfiable, and processing ceases. If some terms of a contradicted constraint are not unconditionally restricted, then the contradiction may be resolved and processing continues.
[0122] Behaviors of Embodiments of the Present Invention
[0123] The following describes behaviors of embodiments of the present invention, and especially how contradictions are resolved according to embodiments of the present invention.
[0124] Problems that are in NP, NP-complete, or NP-hard cannot be solved by deterministic machines unless assumptions are made either explicitly or implicitly. In order that a general algorithm may solve such problems without incurring hyper-polynomial costs and without the need for the algorithm to be tuned to accommodate each specific instance of the problem, the algorithm may exhibit certain behaviors.
[0125] Behavior #1
[0126] One behavior (“Behavior #1”) that may be exhibited by an algorithm to solve problems in NP, NP-complete, or NP-hard without incurring hyper-polynomial costs and without the need for the algorithm to be tuned is such that, when contradictions are found in the rhizomatic networks that are made apparent by the implication of assumptions, these contradictions are moved through the networks in an attempt to assert a value predicate for a term where there is no disagreeing value predicate that is asserted, in order to satisfy all the constraints in the prevailing paths that lead to the contradiction.
[0127] Algorithms that rely on random variations of a putative solution, such as Genetic Algorithms, do not identify the case when there is no solution set at all and are susceptible to performing meandering variations indefinitely when the solution set is small. Algorithms that parameterize contradictions in order to create new summarizing constraints consisting of an indeterminate number of terms risk producing hyper-polynomial numbers of constraints when the order in which assumptions are chosen happens to be pathological or the ordering that determines which assertion becomes prevailing among assertions of identical value predicates happens to be pathological. Avoiding the pathological orderings in algorithms that create summarizing constraints is what tuning should provide; so to provide non-hyper-polynomial cost solutions without tuning, Behavior #1 resolves contradictions while avoiding the creation of new summarizing constraints with an indeterminate number of terms and without relying on random variations.
[0128] In order to describe the motion of contradictions within the rhizomatic network, the following additional definitions are provided.
[0129] Destinations
[0130] In certain embodiments of the present invention, assumptions are non-prevailing but do contribute to the determinant for the variable that the assumption represents. A term that was restricted, but for which there are no extant prevailing assertions that conjunctively converge to produce a determinant that represents the restriction, is either restricted by an assumption or was restricted by a prevailing assertion but that assertion has been subsequently removed, or is restricted in part by an implicated assertion that is not prevailing. Each contradiction must be moved toward a term that is restricted by an assumption or toward some other term for which the recorded restriction is not fully supported by prevailing assertions that are part of a prevailing path that leads to and produces the contradiction. Terms for which the recorded restriction is not fully supported by prevailing assertions are called “destinations”, and destinations that are not fully supported by the conjunctive convergence of extant prevailing assertions and assumptions are called “pseudo-assumptions”.
[0131] Counter-Assertions
[0132] The movement of each contradiction occurs by “counter-asserting” a value predicate for a conditionally restricted term that is in the contradicted constraint.
[0133] Negating
[0134] Counter-asserting resolves the contradiction in one constraint and may “negate” some assertions that contributed to the determinant for the variable represented by the counter-assertion. Negation of an assumptive assertion eliminates the assumption. Negation of an implicated assertion or counter-asserted assertion removes the assertion itself and creates a contradiction in its constraint.
[0135] A counter-assertion may also provide a restriction in a constraint that was not asserting and produce an implicated assertion from that constraint.
[0136] Motion of Constraints
[0137] Any constraint that provided an assertion of a value predicate that represents the variable for which another value predicate is counter-asserted and that disagrees with the counter-asserted value predicate or disagrees with the intersection of the counter-asserted value predicate and other assertions that contribute to the determinant for that variable is negated, thus moving the contradiction from the counter-asserting constraint to contiguous constraints that provided disagreeing assertions. When a destination assumption is negated, or when a value predicate is counter-asserted for a term that was recognized as being restricted but the restricting determinant is not fully supported by prevailing assertions, no contradiction exists in the constraints that embody the prevailing paths of the former contradiction; and as long as Behavior #3 is provided, the contradiction is expelled from the recorded prevailing path of the contradiction, and the expression as a whole may become satisfied if new paths of implication or counter-assertion are not created or found by the negation of an assumption and other contradictions are already expelled.
[0138] Behavior #2
[0139] Another behavior (“Behavior #2”) that may be exhibited by an algorithm to solve problems in NP, NP-complete, or NP-hard without incurring hyper-polynomial costs and without the need for tuning is: (1) for the algorithm to recognize the case in which the counter-asserted value predicate should be unconditional, and (2) for the algorithm not to incur a hyper-polynomial cost in order to recognize when a counter-assertion should be unconditional. Trivially, a counter-assertion must be unconditional if all but one of the terms in the contradicted constraint is restricted unconditionally, and there may be circumstances where conventional mathematical analysis requires that SOMMEs unconditionally counter-assert a value predicate regardless of the existence of destinations; but a counter-assertion of a value predicate for a term in a constraint should also be unconditional when the path of the putative counter-assertion, excluding the sub-paths that provide the prevailing assertions that are putatively negated by the counter-assertion, does not contain any destinations.
[0140] An algorithm that fails to recognize that the expression cannot be satisfied by negating a counter-assertion that should be recognized as being unconditional may retrace a portion of its path an infinite number of times when a problem expression is non-trivially unsatisfiable.
[0141] Behavior #3
[0142] Another behavior (“Behavior #3”) that may be exhibited by an algorithm to solve problems in NP, NP-complete, or NP-hard without incurring hyper-polynomial costs and without the need for tuning is such that the value predicate counter-asserted must not only resolve the contradiction in the counter-asserting constraint, it must also not create a contradiction in any of the constraints in the prevailing path that leads to and produces the counter-assertion, excluding constraints that provided assertions that are specifically negated by the counter-assertion. This behavior requires that the decision of which value predicate to counter-assert has information about the prevailing path leading to and producing the counter-assertion.
[0143] If it is possible that a counter-asserted value predicate creates a contradiction in one or more of the constraints that are in the prevailing path of the counter-assertion, then it is possible that a revision loop may occur that revises the counter-asserted value predicate with a number of loop iterations that is indeterminate, and thus hyper-polynomial, as is the case in approximating algorithms such as the Interval Newton method.
[0144] When many-valued logic is not used by the expression, any conditionally restricted term in the contradicted constraint may be counter-asserted according to the rules of implication, and that counter-assertion is guaranteed to not create contradictions in the constraints in the prevailing path that leads to and produces the counter-assertion.
[0145] Behavior #4
[0146] Another behavior (“Behavior #4”) that may be exhibited by an algorithm to solve problems in NP, NP-complete, or NP-hard without incurring hyper-polynomial costs and without being tuned is such that when multiple paths have equal potential to satisfy the expression by expelling a contradiction, the manner by which the term that is in the contradicted constraint for which a value predicate is to be counter-asserted is chosen must be such that the motion of the contradiction does not retrace paths with a hyper-polynomial number of iterations of the same path nor a hyper-polynomial number of variations of paths.
[0147] Advantages
[0148] Embodiments of the present invention may exhibit any one or more of Behavior #1, Behavior #2, Behavior #3, and Behavior #4, each of which may be implemented using a device, software, or automated process, in any combination. Embodiments of the present invention may be implemented to improve the functioning of a computer itself by providing the benefits described above. Such embodiments achieve their beneficial results using the novel and nonobvious techniques disclosed herein, and therefore do not merely constitute an instruction to apply an abstract idea or to implement an abstract idea on a computer. Embodiments of the present invention which take the form of an improved computer (or one or more components thereof, such as an improved processor) include novel and nonobvious components, such as novel and nonobvious circuits for performing the novel and nonobvious functions disclosed herein. Such novel and nonobvious circuits, by virtue of being novel and nonobvious, are not generic computer components, but instead are components which, as a whole, are unique to embodiments of the present invention, even if they include certain subcomponents (such as certain logic gates) which are known to those having ordinary skill in the art.
[0149] Collectively, the four behaviors listed above are sufficient to solve problems in NP, NP-complete, or NP-hard without incurring hyper-polynomial cost and without tuning. Providing an algorithm that exhibits all four behaviors, even for two-valued logic alone, amounts to proof that P=NP. Considering that the question of whether or not P=NP was formally posed in 1970 and has remained unsolved until now, despite a very significant prize being offered by the Clay Mathematics Institute starting in 2000 and the existence of many regularly scheduled international and regional contests where entrants attempt to solve such difficult problems in minimal time, every device, computer program, or automated process that provides these four behaviors is evidently non-obvious, regardless of what fragmentary technical components exist in the prior art.
[0150] Exhibiting Behavior #1
[0151] Counter-assertion exhibits Behavior #1. It is efficient for contradictions to be resolved in certain sequences. The resolution of one original contradiction is best followed by the resolution of the contradiction produced in a constraint that provided one of the prevailing assertions that were negated by the counter-assertion produced from the original contradicted constraint and so on. The contradictions may be resolved in other orders, but resolving them in this order reduces the number of revisions of the possible means of tracking the paths of prevailing assertions that would otherwise be necessary to providing rigorous accuracy in these tracking elements.
[0152] With rigorously maintained records of the prevailing paths that lead to and produce assertions and counter-assertions, only one such record is needed per asserted value predicate. Without rigorously maintained records, it may be necessary to store a history of all past and present assertions of a specific value predicate or rely on a method that allows dithering to revise the relevant records, as is described farther below. (Explanation of rigorous and lazy maintenance of records is provided farther below, after the nature of those records has been discussed.)
[0153] Persistence of Assertions
[0154] When a first conditional prevailing assertion is such that it was forced by restrictions on the terms of its constraint where those restrictions relied upon other prevailing assertions for support and one or more of those other prevailing assertions have been negated, then the first prevailing assertion may continue to persist. In general, it is better for assertions to persist unless they are explicitly negated, because this eliminates the work of removing and re-propagating assertions; but persistence is not required.
[0155] Exhibiting Behavior #2
[0156] It is necessary to exclude the sub-paths of negated prevailing assertions from the path of a counter-assertion in order to exhibit a behavior that recognizes when a counter-assertion should be unconditional in a non-trivial situation, and this exclusion can be facilitated by tracking the paths that lead to prevailing assertions. Tracking the paths of prevailing assertions is part of the prior art, but some embodiments of the present invention augment the tracking that is in prior art by adding certain elements to the tracking data structure.
[0157] Full Reasons of Implicated Assertions
[0158] In certain embodiments of the present invention, each prevailing assertion records a “full reason” that contains the value predicates of previous assertions that restricted terms in the constraints of the prevailing paths that led to and produced the current prevailing assertion, and each value in a full reason is augmented with counts. One such count is the “fulfilled” count.
[0159] To explain how the fulfilled count accrues during implication when there are no other counts:
an assumption has an empty full reason; and a candidate implicated prevailing assertion has a full reason that contains the union of the set of value predicates in the full reasons for all extant prevailing assertions that are not unconditional and which conjunctively converge to produce determinants that restrict terms in the constraint from which the candidate assertion derives, unioned with the set of value predicates of the assertions that are not unconditional and which restrict terms in the constraint from which the candidate assertion derives; and when a specific value predicate in the full reason of the candidate assertion derives from exactly one of the unioned previously populated full reason, then the fulfilled count for that value predicate is inherited from the previously populated full reason from which it derives; and when a specific value predicate in the full reason of the candidate assertion derives from a previously populated full reason and is shared between two or more of these unioned previously populated full reasons, then the fulfilled count is the sum of the corresponding fulfilled counts derived from previously populated full reasons; and when a specific value predicate in the full reason of the candidate assertion does not derive from any of the unioned previously populated full reasons, the fulfilled count for this value predicate is initialized as being equal to zero; and the fulfilled count for any value predicate in the full reason of the candidate assertion is incremented by one for each value predicate in the set of value predicates of the assertions that are not unconditional and which restrict terms in the constraint from which the candidate assertion derives.
[0166] The fulfilled count is a way of encoding predecessor prevailing assertions in prevailing paths that led to and produced a single resultant first prevailing assertion. The counts in this encoding permit the prevailing path of a second prevailing assertion to be subtracted from the full reason of the first prevailing assertion without removing any sub-paths that may be common to the prevailing paths of other prevailing assertions that led to and produced the first prevailing assertion. This capability is useful for the proper analysis of the prevailing paths of restricting prevailing assertions in order to decide which restricted terms may be counter-asserted and which counter-assertions must be unconditional.
[0167] Farness Counts
[0168] Behavior #2 may be exhibited by some means that provides an ordering of the restricted terms that are in the path that leads to and produces a counter-assertion so that, when accessed in either ascending or else descending order, a candidate assertion in the path is always encountered (by way of the term ordering) before encountering any of the assertions that led to and produced that candidate assertion. “Farness counts” provide such an ordering. Farness counts or some other means of providing this ordering may be employed to exhibit Behavior #2. “Maximum distance counts” and carefully maintained prevalence numbers are considered to be farness counts. Insofar as prevalence numbers may be used as farness counts, the language used when referring to the ordering of farness counts will assume that ascending order of farness counts indicates increasing farness, even though the descending order typically provides such an ordering for prevalence numbers.
[0169] Each maximum distance count records the maximum distance between a resultant conditional prevailing assertion and each value predicate in the full reason of the resultant assertion, where “distance” in this context reflects the number of implicational or counter-assertion steps between value predicates and the resultant conditional prevailing assertion. In certain embodiments of the present invention, the maximum distance counts in the full reason for a non-assumptive resultant conditional prevailing assertion are constructed as follows:
[0170] When the full reason of the resultant assertion is being accrued, all the maximum distance counts that derive from the full reasons of previous assertions are incremented by one, and value predicates that do not derive from a full reason are given a maximum distance count equal to one, and then the single maximum distance count that is the greatest among all the maximum distance counts for the same value predicate in the union that produces the set of value predicates in the full reason of the resultant is identified and assigned as the maximum distance count for the corresponding value predicate in the full reason of the resultant assertion. (Assumptions have no full reasons and therefore can have no distance counts in their putative full reasons.)
[0171] Unfulfilled Counts
[0172] A non-necessary count that may be used by embodiments of the present invention is the “unfulfilled” count. When unfulfilled counts are used, the manner of accruing the fulfilled count is different than described above, but the manner of accruing the maximum distance counts is the same as above.
[0173] To explain how the unfulfilled count accrues and how the fulfilled count accrues when unfulfilled counts are used in the full reason of a given implicated conditional prevailing assertion:
[0174] (This process description, as well as others farther below, includes bracketed statement labels such as “[U1]”. These labels uniquely identify the statements and explicitly reiterate the nesting of statements relative to qualifying statements that is normally indicated by indenting of text in pseudo-code. Without an indication of nesting, the description may be interpreted ambiguously.)
[0175] [U1] The “basis” of the resultant full reason is initialized as empty.
[0176] [U2] If there is exactly one implicated conditional prevailing assertion that restricts a term in the constraint of the given assertion:
[U2a] The contents of the full reason of this one implicated conditional prevailing assertion is copied as the basis; and the value of the assertion itself is added to the basis, and that value is associated with a fulfilled count of one and an unfulfilled count of zero.
[0178] [U3] If there is more than one implicated conditional prevailing assertion that restricts one or more terms in the constraint of the given assertion:
[U3a] The content of the full reason of one implicated conditional prevailing assertion is copied as the basis and this prevailing assertion is then ignored by further processing. [U3b] For each candidate implicated conditional prevailing assertion that restricts a term in the given constraint and which is not yet ignored by further processing:
[U3b1] If the value predicate of the candidate assertion appears in the basis:
[U3b1a] Increment the unfulfilled count for the value of the candidate assertion in the basis by one, and the candidate assertion is ignored by further processing.
[U3b2] Otherwise:
[U3b2a] Copy the full reason of the candidate assertion as the “co-basis”. [U3b2b] For each candidate value predicate in the co-basis that has a non-zero fulfilled count, in ascending maximum distance count order:
[U3b2b1] If the candidate value predicate appears in the basis, subtract the fulfilled and unfulfilled counts associated with all value predicates in the full reason of the prevailing assertion of the candidate value predicate from the co-basis, and subtract one from the fulfilled count of the candidate value predicate in the co-basis, and add one to the unfulfilled count of the candidate value predicate in the co-basis. [U3b2b2] Remove every value predicate that has fulfilled and unfulfilled counts that are both zero from the co-basis.
[U3b2c] Add the value predicates in the co-basis to the basis where they do not already exist, and add the fulfilled and unfulfilled counts from the co-basis to the corresponding fulfilled and unfulfilled counts in the basis, and add the value predicate of the candidate assertion to the basis with a fulfilled count of one and an unfulfilled count of zero, and the candidate assertion is ignored by further processing.
[U3c] For each value predicate of an assumption or a conditional non-prevailing assertion that contributes to the determinants that restrict one or more terms in the given constraint:
[U3c1] If the value predicate of the candidate assertion appears in the basis:
[U3c1a] Increment the unfulfilled count in the basis that is associated with the value predicate of the candidate assertion by one.
[U3c2] Otherwise:
[U3c2a] Add the value predicate of the candidate assertion to the basis, associated with an unfulfilled count equal to one.
[0194] [U4] Use the basis as the full reason of the assertion of the given constraint.
[0195] The method of accruing fulfilled and unfulfilled counts described above is a means of compressing the information that is present when fulfilled counts are used and unfulfilled counts are not used and which is necessary to permit the subtraction of a portion of the path behind a prevailing assertion (when this prevailing assertion disagrees with the counter-assertion) without also subtracting sub-paths that are common to the paths of other prevailing assertions that produce the resultant counter-assertion.
[0196] When unfulfilled counts are not used, the maximum number of bits required in order to represent each fulfilled count is equal to the number of variables in the expression. When unfulfilled counts are used in the manner described above, the number of bits required in order to represent each fulfilled count is one, and the number of bits required in order to represent each unfulfilled count is the base-2 logarithm of the number of constraints in the expression, which is usually a significant reduction in the number of switches required to represent the counts and the costs to operate those switches.
[0197] Maintaining the Order of Subtractions from the Basis
[0198] It is possible to use prevalence numbers instead of maximum distance counts to order the subtraction of prevailing assertions from the basis, but this requires that prevalence numbers consistently act as farness counts and therefore provide an ordering of assertions that prevents the removal of prevailing assertions that appear in sub-paths that are shared between the prevailing paths of other prevailing assertions that must have their full reasons subtracted from the basis and assertions that need not have their full reasons subtracted from the basis. The initial ordering of prevalence numbers is sufficient for them to perform as farness counts when accessed in descending order rather than ascending order, but prevalence numbers are reassigned when terms are counter-asserted, which disturbs the original ordering. Consequently, using prevalence numbers as farness counts usually requires significant revision of the prevalence numbers, which makes the amount of computational work required similar to that which is required when maximum distance counts are used as the farness counts.
[0199] Branch-Subtraction
[0200] It is noteworthy that neither the compressed nor the uncompressed version of full reason, whether the expression uses two-valued logic or many-valued logic, is equivalent to either a list of the restricted terms in a path or a list of the restricting values in a path, each associated with a count of the number of terms restricted by that value. Such counts or implicit counts do not support “branch-subtraction” in a rhizomatic network. The truth of this statement should become apparent by comparing the behavior of the different kinds of counts as they would be manipulated by the method of branch-subtraction which is described below.
[0201] In branch-subtraction, when a minuend full reason does not contain the value predicate of a subtrahend assertion, then the branch-subtraction difference is identical to the minuend. Otherwise, the branch-subtraction difference is the result of the following computations:
[0202] [B1] If unfulfilled counts are being used:
[B1a] For each value predicate in the minuend, subtract from each of the corresponding minuend counts the fulfilled count and unfulfilled count associated with the identical value predicate that is in the full reason of the subtrahend assertion. [B1b] Subtract one from the associated fulfilled count and add one to the associated unfulfilled count where the value predicate of the subtrahend assertion is in the minuend.
[0205] [B2] Otherwise:
[B2a] Identify the fulfilled count in the minuend that is associated with the value predicate of the subtrahend assertion and call this the “scalar” value. [B2b] For each value predicate in the minuend, subtract from the associated minuend fulfilled count the product of the scalar and the fulfilled count associated with the identical value predicate that is in the full reason of the subtrahend assertion.
[0208] [B3] After the subtractions above, remove any value predicates from the minuend that have zero in all existing counts, and present the result as the difference of the branch-subtraction.
[0209] Embodiments of the present invention may include the ability to distinguish whether a portion of a path contains a destination in order to exhibit Behavior #2. The ability to distinguish destinations and therefore count the distinct destinations in a portion of a path can also be very useful. Branch-subtraction can supply both these abilities.
[0210] Branch-subtraction without the use of unfulfilled counts requires multiplication for every subtracted value predicate in each full reason where branch-subtraction occurs. Multiplication has a computational cost that is the square of the number of bits being multiplied, and this represents another significant computational cost that is incurred when unfulfilled counts are not used.
[0211] Full Reasons in the Presence of Counter-Assertions
[0212] The existence of counter-assertions complicates the accrual of reasons for some assertions because negation of assertions removes the reasons for those assertions, and a counter-assertion may create a new reason for an assertion that was previously negated. The reasons of prevailing assertions that are being used to make decisions about the direction of motion of the point of contradiction must be consistent in order for the decision to be made correctly or consistently. Therefore, before such a decision can be made, the reasons of assertions that depend on assertions that were negated in order to make those reasons consistent may be re-computed. When nearness counts (see farther below as part of Exhibiting Behavior #4) are not used, reasons that depend on assertions that were negated may be re-computed by performing branch-subtraction for negated prevailing assertions and by performing branch-addition of the new reasons, when formerly negated assertions are counter-asserted. When performing branch-addition for this purpose, the farness counts of the re-asserted value predicate may be added to the farness counts in the added branch. Furthermore, any formerly conditional prevailing assertions that have recently become unconditional may be branch-subtracted, and the unconditional assertion itself may be removed from all full reasons.
[0213] Back-Tracking
[0214] When distance counts are being used, it may be necessary to “back-track” through the constraints in the path of an assertion that needs its reason re-computed rather than using branch-subtraction to revise the reason. This manner of back-tracking is similar to the one described below, but the reasons of assertions that restrict terms and have already been re-computed are branch-added and their counts are incremented, but these assertions are not explored by the depth-first mechanism.
[0215] It is possible to re-compute distance counts without back-tracking, but this requires separate distance counts for each contributing sub-path or else a count of instances of each distance count value, which would consume significantly more space than an uncompressed full reason consumes.
[0216] It is possible to exhibit Behavior #2 without using full reasons by using depth-first stack-based back-tracking through the restricted terms in the constraints that constitute the prevailing path that leads to and produces the counter-assertion. Depth-first back-tracking ensures that the attributes of prevailing assertions are revised in an order that is equivalent to descending farness order. This method ignores all terms that are restricted only by unconditional assertions, and ignores all terms that are restricted by assertions that have already been considered, and notes those terms that are destinations, including terms that are negated by loop assertions, and excluding illegitimate pseudo-assumptions (see farther below); and for each other term, stacks for consideration the conditionally restricted terms in the constraints of prevailing assertions that restrict the given term in a way that ensures depth-first traversal.
[0217] Back-tracking need not use permanently stored reasons. In such a case, there is no opportunity to revise reasons rigorously or otherwise. If permanently stored reasons are not being used, then temporary lists of destinations and possibly their distances must be maintained for each constraint the terms of which are stacked, and these temporary lists of destinations should be summed into the temporary destination lists for the constraints of dependent assertions as the terms restricted by the assertions are popped from the stack, and illegitimate pseudo-assumptions should be identified and eliminated at the time that disagreeing terms are popped from the stack. Temporary lists of destinations should be deleted after each contradiction is resolved. If destination lists are not deleted, then to be useful they will have to be revised, and in order for it to be possible to revise them without completely replacing them, they must contain non-destination terms or assertions, making them become reasons of some kind. It is possible to stack restricting assertions rather than terms for the purpose of back-tracking.
[0218] Because assertions get negated by counter-assertions, it is necessary to record the restrictions for terms in SOMMEs when full reasons are not being used, because the restricting determinants and assertions may no longer exist. Restrictions need not be recorded for terms in strictly disjunct phrases, because a missing restriction can be presumed to be the complement of the value predicate that the term represents in such a constraint, and indeed it may be more efficient to always record restrictions in this way for disjunct phrases.
[0219] Rigorous Maintenance of Prevailing Paths
[0220] When full reasons are being used and the path of a prevailing assertion is to be used for decision-making, it is necessary to re-compute the full reason of the candidate prevailing assertion. In order to maintain full reasons “rigorously”, it is necessary to re-compute the full reasons of every prevailing assertion that depends on a negated prevailing assertion at the times of negation and counter-assertion.
[0221] At the time that full reasons are used for decision-making, the existence of pseudo-assumptions in the prevailing path must be recognized, if any. If unfulfilled counts are not being used, then branch-subtraction, as described, would incorrectly eliminate any record of pseudo-assumptions; so in this case, either an alternate method that marks pseudo-assumptions in some other way or back-tracking may be used. If unfulfilled counts are used and the full reasons of the negated prevailing assertions are not branch-subtracted from every full reason, then a decision-making method that uses dithering of the motion of a contradiction may be used to revise the full reasons and other path tracking elements to a state that is a useful approximation of a rigorous current state, as is described farther below.
[0222] Similarly, the value predicates asserted by constraints in a prevailing path must be consistent at the time a decision about the value predicate of a new counter-assertion is made. For disjunct phrases, no special action is necessary because such constraints either assert a pre-defined value predicate for a specific variable or do not make an assertion of that variable at all. However, in the case of SOMMEs, a change in a restricting value predicate may result in a change in the value predicate asserted or counter-asserted that has a prevailing path that includes the revised restriction, and these revisions need to be propagated through the prevailing path of any new counter-assertion. If conventional mathematical analysis does not supplement the present invention, then Behavior #3 may be violated if the assertions of SOMMEs are maintained rigorously, i.e. at the time of negation; so the revision of value predicates of SOMMEs when there is no conventional mathematical analysis is best propagated lazily, as described immediately below, or not propagated except by dithering, which is explained farther below as part of the discussion of exhibiting Behavior #4.
[0223] Lazy Maintenance of Full Reasons
[0224] When full reasons are not maintained rigorously, the full reasons may contain value predicates that have a zero fulfilled count, even while there is a prevailing assertion of that predicate. If any such value predicates exist in a full reason, the candidate full reason should be revised by branch-adding the missing reasons so that they then have a non-zero fulfilled count. If nearness counts (see farther below) or farness counts are to be used, then they must be correct at the time they are used (in the basis and co-basis, for example), and those counts should be re-computed when prevailing assertions exist but are not recorded in the full reason of a counter-assertion.
[0225] Re-computation of counts is most efficiently accomplished by depth-first back-tracking through the affected constraints, and then re-computing the farness counts or nearness counts (see farther below as part of Exhibiting Behavior #4) for the assertions of each of the affected constraints in reverse back-track order. When back-tracking is used only for re-computation of counts, it may occur on an as-needed basis. However, if full reasons are not being used to provide Behavior #2, then it is most efficient to perform a complete back-track and identify assumptions and pseudo-assumptions at the same time as farness or nearness counts are re-computed.
[0226] Pseudo-Assumptions, Loops, and Teardrops
[0227] When the full reason of a candidate prevailing assertion contains a value predicate for the same variable that is represented by the candidate prevailing assertion itself, there are a number of possible cases: the assertion may disagree with a value predicate in its full reason; the assertion may represent a value predicate that is a subset of a value predicate in its full reason (i.e. the counter-assertion “agrees” with a value predicate in its full reason); or some other relationship applies. These relationships define “loop” and “teardrop” paths and affect the definition of a legitimate destination.
[0228] Pseudo-Assumptions
[0229] When a counter-assertion occurs, assertions are negated, and consequently, the prevailing assertions that provide restrictions to terms in the paths of other prevailing assertions may go missing. When a rigorously maintained full reason contains a value predicate for which there is no extant prevailing assertion, we call that value predicate a “pseudo-assumption”. Assumptions and pseudo-assumptions are destinations toward one of which a contradiction should move. Destinations are terms in constraints of the prevailing path of an assertion such that if a contradiction is moved to that constraint and the destination term is counter-asserted, the contradiction is expelled from the constraints of the recorded prevailing path.
[0230] No Destinations Rule
[0231] In order for embodiments of the present invention to exhibit Behavior #2 correctly, it is desired that any assertion that has a full reason and has no destinations in its full reason should be unconditionally asserted. This is the “No Destinations” rule. When a full reason of an assertion contains a value predicate for the same variable as the assertion itself, distinctions are provided by the present invention in order to implement the No Destinations rule to correctly produce unconditional assertions, as follows.
[0232] Loops
[0233] If an assertion agrees with a value predicate in its full reason, then we say that a “loop” exists in the prevailing path of this assertion. The structure of a loop is such that if an assertion in the looped prevailing path is negated, the contradiction that is produced may go around the loop to assert a value predicate that agrees with the negating counter-assertion, causing the contradiction in the loop to be resolved, effectively expelling the contradiction from the prevailing path of the loop without necessarily creating a new contradiction in some other path. Consequently, the start of a loop is a destination. If the assertion that completes a loop were to be prevailing, then it might be considered to support the restriction that starts the loop, which would provide a full reason for the assertion that completes the loop, and that full reason could contain no destinations, suggesting that it be interpreted as an unconditional assertion. That interpretation would be incorrect; so some additional rule or indication is necessary in order to ensure that loop assertions are not interpreted as unconditional assertions.
[0234] In certain embodiments of the present invention, an assertion that completes a loop is made to be non-prevailing, regardless of whether prevailing assertions for the same variable are extant or non-extant, but does contribute its value predicate to the determinant for the variable it represents, if the existing determinant does not represent a subset of the atomic values represented by the loop assertion. As a consequence of this, a loop cannot provide destination-free reasons for its own assertions and therefore a prevailing path that depends on a loop always apparently represents a destination in that path. (This rule prevents a loop assertion from having a reason, and therefore may be seen as a method of explicitly avoiding circulus in probando and thus avoids any appearance of a valid disagreement with the complement of the loop assertion.) In other embodiments of the present invention, loop assertions may be explicitly marked in other ways and treated as destinations by those other methods of marking.
[0235] Teardrops
[0236] If every value predicate in the full reason of a counter-assertion that represents the same variable as the assertion itself also disagrees with the value predicate represented by the assertion, then we say that a “teardrop” exists and is identified in the prevailing path of the counter-assertion. The “precipitant” of a teardrop is a value predicate that is known to represent a set of atomic values such that, if any such atomic value were asserted and the set of constraints that are in the prevailing paths of which the teardrop consists do not already contain a contradiction, the assertion would necessarily produce a contradiction in one of these teardrop constraints, regardless of the order in which assertions are propagated. The precision of a precipitant depends upon the information that is available in the prevailing path of the counter-assertion.
[0237] Precipitants
[0238] When all the constraints of which a teardrop consists that also have terms of the same variable as the precipitant of that teardrop are disjunct phrases, then the precipitant must disagree with each of these terms and is therefore the complement of the union of the value predicates represented by these terms. A counter-assertion that allows us to identify a teardrop must represent a subset of the atomic values that are in the complement of the precipitant of its teardrop.
[0239] When the set of constraints of which a teardrop consists and that also have terms of the same variable as the precipitant of that teardrop includes SOMMEs, then the precipitant must be the complement of the counter-asserted value predicate intersected with the restrictions on these terms.
[0240] If a putative precipitant is computed as above and the complement of the putative precipitant is an empty set of atomic values, then the putative teardrop is not in fact a teardrop and some legitimate destinations for the variable of the so-called precipitant must exist.
[0241] Counter-Asserted Value Predicates
[0242] If full reasons are being used, the branches for prevailing assertions that are negated by a counter-assertion are subtracted from the full reason of the counter-assertion. After these branch subtractions, if there are no destinations in the prevailing path of the counter-assertion for variables other than the variable of the precipitant, then the complement of the precipitant should be asserted unconditionally. If the value predicate of this unconditional assertion is the same set as the value predicate of the counter-assertion as produced by the rules of Implication, then the unconditional assertion is the only value predicate that is counter-asserted; otherwise, both the unconditional and conditional assertions are produced by the counter-assertion. If no teardrop is identified and the counter-assertion is not trivially unconditional, then the counter-assertion produces only a conditional assertion.
[0243] Apparent Pseudo-Assumptions in Teardrops
[0244] When a precipitant is being negated by the counter-assertion that defines it, the assertions that support the restriction that is the precipitant will be negated by the counter-assertion and the reasons for those branches will be subtracted from the full reason of the counter-assertion, thus making the terms that are restricted by these assertions be pseudo-assumptions and appear to be destinations. If the full reason of a counter-assertion that negates a precipitant contains no other destinations, then the counter-assertion should be unconditional because unconditionally asserting the precipitant would create an unconditional contradiction in the teardrop. Consequently, the restrictions recorded in the full reason of a counter-assertion that represent the same variable as the counter-assertion itself and which disagree with the counter-assertion should not be treated as destinations despite being pseudo-assumptions and are “illegitimate” destinations.
[0245] If a counter-assertion negates the precipitant of the teardrop that the counter-assertion identifies, and there are no legitimate destinations in the full reason of the counter-assertion, then the counter-assertion is unconditional; and unconditional assertions do not have reasons. If a counter-assertion negates its precipitant, and there are legitimate destinations in the full reason of the counter-assertion, then the counter-assertion is conditional; and although restrictions for terms of the same variable will appear in the full reason as pseudo-assumptions, other destinations will also be present in the prevailing path. If a contradiction moves toward any of these destinations, including the illegitimate destinations, a value predicate that includes some atomic values that are in the precipitant must be asserted, and this assertion is effectively a partial re-assertion of that precipitant. If the determinant produced by incorporating this value predicate that partially re-asserts that precipitant also fully supports any of the restrictions on terms of the same variable as our predicate-negating counter-assertion that were represented by the restricting value predicates in the full reason of the precipitant-negating counter-assertion, then the assertions that support those restrictions will provide their reasons to the full reasons of assertions that are led to and produced by these restrictions, and these restrictions will no longer appear to be pseudo-assumptions. If the determinant produced by incorporating this value predicate that partially re-asserts that precipitant does NOT fully support a restriction on a term of the same variable as our predicate-negating counter-assertion that is represented by a restricting value predicate in the full reason of the precipitant-negating counter-assertion, then the lack of extant prevailing assertions to support the restrictions on those terms will make those restrictions become legitimate destinations for the contradiction produced by the counter-assertion that produces the partial re-assertion of the precipitant. So a special rule that eliminates some pseudo-assumptions as being illegitimate destinations is only required when producing, and in order to correctly produce, a non-trivially unconditional counter-assertion, unless a Nearest Destination method is being used. (Nearest Destination methods are explained farther below as part of Exhibiting Behavior #4, and the complication for teardrop pseudo-assumptions when a Nearest Destination method is being used appears in the discussion of Dithering farther below.)
[0246] It is noteworthy that a first assertion that is in the prevailing path of a second prevailing assertion is always nearer to the second prevailing assertion than any illegitimate destination that the first assertion may have created.
[0247] Characterization of the Motion of Contradictions
[0248] A contradiction can be characterized as a disagreement of assertions between multiple rhizomatic networks that may have common network segments. By counter-asserting one of the disagreeing assertions, its network grows; and when the disagreeing assertions are negated, their networks shrink. Whether counter-assertion incorporates branch-subtraction of full reasons of the negated prevailing assertions or back-tracks through the new networks, the incorporated operation ensures that destinations that are strictly ahead of the counter-assertion are not represented as being in the network of the counter-assertion and therefore do not misinform the methods of embodiments of the present invention that exhibit Behavior #2 and Behavior #4.
[0249] Efficiency of the Methods of Behavior #2
[0250] The efficiency of the methods that exhibit Behavior #2 may be affected by two factors that have not yet been fully discussed: parallelization of the process of resolving contradictions, and prevalence of assertions.
[0251] The nature of teardrops is such that horizontal parallelization of the process of resolving constraints in the form of multiple processes simultaneously attempting to resolve contradictions can interfere with Behavior #2 to a degree that is moderate to severe. A first contradiction moving in parallel with a second contradiction could produce a counter-assertion resulting from the first contradiction that causes a term in the full reason of a counter-assertion resulting from the second contradiction to become a pseudo-assumption, when otherwise the prevailing path of the restriction on that term would permit the counter-assertion resulting from the second contradiction to be unconditional. Various efforts might be made to counteract this interference.
[0252] One method of counteracting interference between parallel contradiction resolution processes is to have each process record a separate set of full reasons that can persist when one counter-assertion erases the history of another counter-assertion, but which erases existing full reasons and cross-populates a replacement full reason into the separate stores of parallel contradiction resolution processes whenever a new full reason is generated by any of these processes. Obviously, this method requires a large increase in the amount of data stored.
[0253] Another method of counteracting interference between parallel contradiction resolution processes is to rank the contradictions so that no counter-assertion resulting from a first contradiction will be permitted if it would erase the history of paths being used by a second contradiction of higher rank, thus effectively suspending the motion of the first contradiction. This method can be improved by altering the ranks of contradictions so that suspended contradictions have their ranks lowered; otherwise a cascade of suspensions could occur, effectively reverting the algorithm to a non-parallelized condition. Great care would be necessary in order to formulate a re-ranking that was guaranteed to prevent hyper-polynomial dithering. (See farther below for a discussion of dithering.)
[0254] Prevalence of assertions affects the efficiency of the methods that exhibit Behavior #2 positively. By having prevailing paths that are distinct from additional paths that also converge conjunctively to produce a determinant that represents the same value predicate, the present invention avoids a hyper-polynomial explosion of possible paths that would need to be checked to discover whether any of those paths defined a teardrop and permitted an unconditional counter-assertion. Instead, paths are searched incrementally as long as extant contradictions that are dependent on those paths remain unresolved, in which case the unresolved contradictions provide new prevailing assertions with new paths that re-restrict terms that were formerly pseudo-assumptions. This is a form of path search that will terminate in polynomial time if Behavior #4 is exhibited.
[0255] Exhibiting Behavior #3
[0256] For counter-assertions that have prevailing paths that do not contain SOMMEs, enabling an algorithm to exhibit Behavior #3 is trivial if the algorithm has already been enabled to exhibit Behavior #2: immediately after the time of counter-assertion, the only constraints that contain new contradictions are those that had assertions which were negated by the counter-assertion, and the prevailing paths of negated assertions are subtracted from the prevailing path of the counter-assertion or ignored during a back-track of the prevailing path of the counter-assertion; so those contradictions do not appear in the prevailing path of the counter-assertion.
[0257] For counter-assertions that have prevailing paths that include SOMMEs, exhibiting Behavior #3 is more complicated. Generally, when SOMMEs exist in an expression, and the variable of the term for which a value predicate putatively should be counter-asserted is the same as the variable of one or more terms in the prevailing path of the putative counter-assertion, then special methods must be employed to efficiently exhibit Behavior #3.
[0258] When the values of variables represent integers or other rational numbers with a fixed maximum numerator and maximum denominator, then SOMMEs that are closed for the rational numbers may be replaced with a number of intermediate variables and disjunct phrases that represent the numbers digitally and reproduce the behavior of the SOMMEs for rational numbers. The order of magnitude of the count of intermediate variables or constraints in such a case depends on the specific function being reproduced. Adders have a linear count of elements; multiplication has a squared count of elements relative to the number of bits in the multiplication; and so forth.
[0259] Similarly, when the values of variables represent integers or other rational numbers with a fixed maximum numerator and maximum denominator, and it is acceptable that SOMMEs that are not closed for the rational numbers are allowed to produce estimated results, then too each of these SOMMEs may be replaced by a collection of intermediate variables and disjunct phrases.
[0260] Replacing a SOMME with intermediate variables and disjunct phrases permits the behavior of the SOMME to be produced directly as a product of the present invention, and Behavior #3 will be provided as for two-value logic. When SOMMEs are not replaced, it becomes possible that the introduction of a single-value determinant should force two or more other assertions from a set of unreplaced SOMMEs without one depending on the other and without any other intermediate assertions. If the behavior of the present invention is used to analyze such a structure, a hyper-polynomial number of revisions of variable values may occur; so it is necessary to supplement the present invention with conventional mathematical analysis in order to efficiently produce an acceptable result for such a structure. Such a supplementation may require that multiple value predicates are simultaneously revised and therefore asserted, and the nature of the relationship between SOMMES may require that some value predicates are unconditionally asserted even though assumptions exist in the prevailing path; but as long as the prevailing path is still recorded or is still reconstructable, then the present invention can successfully use conventional mathematical analysis as a black box function.
[0261] Exhibiting Behavior #4
[0262] Behavior #4 may be exhibited by having some means by which a specific prevailing path on which the contradiction will travel can be chosen and that choice is, by the nature of the means with which it is chosen, not subject to a hyper-polynomial number of revisions.
[0263] When only one term in a contradicted constraint is restricted by a conditional assertion, the contradicted constraint must be made to unconditionally counter-assert a value predicate of the variable of that one term. When two or more terms in a contradicted constraint are restricted by conditional assertions, the contradicted constraint must be made to counter-assert a value predicate of the variable of one of these terms, and this counter-assertion is conditional unless it is clear that there are no legitimate destinations in the prevailing path leading to this counter-assertion, as was discussed above.
[0264] In an embodiment of the present invention where only one processor operates on the expression, there is no reason to distinguish between formal assumptions and pseudo-assumptions that are legitimate destinations when making a choice of term for which a value predicate should be counter-asserted. However, when there are multiple processors, in other words, when the processing has been parallelized, it is preferable to move the contradiction in the direction of formal assumptions and suspend processing for contradictions that have only pseudo-assumptions in their full reasons and those pseudo-assumptions are not created by unconditional counter-assertions or in uncontroversial variables. Otherwise, it is possible for one contradiction to move toward a pseudo-assumption only to have the direction of motion reversed when the parallel motion of another contradiction that had created the pseudo-assumption is not successfully expelled and then re-asserts the value predicate that had been negated in order to form the pseudo-assumption, in which case, the motion of the given contradiction was wasted computational work.
[0265] Problems that are similar to those created by parallelized processing may become apparent if contradictions are not moved through the rhizomatic network in sequence. Consequently, it is desirable to maintain a stack or other ordered pool of contradictions to be resolved so as to ensure that the contradictions are resolved in a sequence that limits interference. A convenient sequence is to resolve a contradiction in a candidate constraint where the most recent counter-assertion negated the assertion of that candidate constraint immediately after resolving the contradiction in the counter-asserting constraint and to continue resolving contradictions according to their proximity to the most recent of the increasingly historic counter-assertions that created contradictions that have not yet been resolved.
[0266] Nearest Destination
[0267] One of the simplest ways to enable an algorithm to exhibit Behavior #4 when Behaviors #1 and #3 have already been enabled to be exhibited is by using a “Nearest Destination” method. Nearest Destination methods identify a destination that is “nearest” to the contradiction.
[0268] Nearness Counts
[0269] In certain embodiments of the present invention, a nearest destination is identified by comparing “minimum distance counts”. Minimum distance counts are very similar to maximum distance counts except that they represent the least count among the minimum distance counts associated with the identical value predicates being unioned rather than the greatest count among maximum distance counts.
[0270] In other embodiments of the present invention, a nearest destination is identified by comparing “restriction counts”. The advantage of restriction counts over minimum distance counts is that they provide a more extensive estimate of the computational work incurred by moving the contradiction to its destination. Restriction counts in the full reason for a resultant conditional prevailing assertion are constructed as follows:
[0271] When the full reason of the resultant assertion is being accrued, all the restriction counts that derive from the full reasons of previous assertions are identified, and unioned assertions not in these full reasons are given a restriction count that is equal to the number of constraints that would be restricted by a counter-assertion of a value predicate for the term in the constraint of the resultant assertion that is restricted by that assertion, and then the single minimum restriction count among all the restriction counts for the same value predicate in the union that produces the set of value predicates in the full reason of the resultant is identified and the number of constraints that would be restricted by a negation of the resultant assertion is added to each of the identified counts before each is assigned as the restriction count for the corresponding value predicate in the full reason of the resultant assertion.
[0272] In other embodiments of the present invention, a nearest destination is identified by comparing “work counts”. The advantage of work counts over restriction counts is that they provide a better estimate of the computational work that may be incurred by moving the contradiction to its destination. Work counts in the full reason for a non-assumptive resultant conditional prevailing assertion are constructed as follows:
[0273] When the full reason of the resultant assertion is being accrued, all the work counts that derive from the full reasons of previous assertions are identified, and unioned assertions not in these full reasons are given a work count that is equal to the number of constraints that could become contradicted or asserting as a result of a counter-assertion of a value predicate for the term that is restricted by that assertion, and then the single minimum work count among all the restriction counts for the same value predicate in the union that produces the set of value predicates in the full reason of the resultant is identified and the number of constraints that would become contradicted or asserting as a result of a negation of the resultant assertion is added to each of the identified counts before each is assigned as the work count for the corresponding value predicate in the full reason of the resultant assertion.
[0274] Because the number of constraints that would become contradicted or asserting may be affected by parallel constraint resolution processes, work counts may have to be re-computed in order to avoid dithering in that case. This extra computational cost would probably eliminate much of the advantage that work counts might otherwise provide. Also, when an expression uses many-valued logic, it may not be possible to accurately determine the number of constraints that would become contradicted or asserting as a result of a counter-assertion, because the value of the counter-assertion may not be entirely predictable.
[0275] “Nearness counts” is the name that generalizes the set of counts that are exemplified above as minimum distance counts, restriction counts, or work counts. Other kinds of nearness counts are possible, but any valid nearness count should support a Nearest Destination method by providing an ordering of directions in which to move a contradiction that persists or becomes more emphatic after the contradiction has moved if the counts are maintained rigorously, as do the example nearness counts described above.
[0276] Counter-asserting a value predicate for the restricted term that provides the least nearness count for a valid destination and negating the prevailing assertions that restrict the term of the counter-assertion when nearness counts are rigorously maintained will cause the nearness count associated with the chosen destination in the full reason of the prevailing assertion that is being negated by the counter-assertion to become less for the next counter-assertion than it was before, as the contradiction moves from constraint to constraint; and the nearness counts for all other paths to the chosen destination will often increase but can decrease by an increment that is identical to the decrease in the nearness count of the currently chosen path to the destination at most, which leaves the nearness ordering of the various paths to the chosen destination intact or even more emphatically preferring the selected path. So in such cases, the contradiction will move toward the chosen destination without ever retracing a path.
[0277] Dithering
[0278] If nearness counts are not rigorously maintained, then the motion of the contradiction may dither when a Nearest Destination method is being used. When a contradiction moves toward a chosen destination and then it is revealed that the chosen destination is no longer in the path in that direction or it is actually farther to the chosen destination along this path than it appeared, and a different path to the same destination is nearer relative to the revealed distance along the current path, or a different value predicate is chosen as the destination, then the direction of motion of the contradiction changes. This change of direction could be opposite to the direction recently traversed, resulting in “dithering”, meaning that the contradiction would re-traverse some of the same constraints, possibly returning to its original position before moving toward the newly preferred destination. However, in this case, the nearness counts for the original destination and other destinations in the same path will be updated as the contradiction moves away from the point where it was revealed that the preferred destination is not most expeditiously reached along the original path. This means that if the direction of motion of the contradiction is again reversed, there will be no revelation at or prior to the point where a revelation of a change in the nearest destination was found the first time that the direction of motion was reversed. Consequently, the contradiction will eventually reach one of the destinations, possibly retracing a central chain of constraints back-and-forth a number of times that is limited by the number of constraints in the expression that could record revelations about the nearest destination. So pursuing a chosen destination along the path that provides the least nearness count when nearness counts are not rigorously maintained still produces behavior that does not have a hyper-polynomial cost, even though the method is significantly less efficient than a similar method where the nearness counts are maintained rigorously.
[0279] It is possible for infinite dithering to occur when a Nearest Destination method is being used, because illegitimate destinations in a teardrop may be nearer to the contradiction than any legitimate destinations. If illegitimate destinations are nearer to the contradiction in more than one direction, then the contradiction will move toward one illegitimate destination until the precipitant of its teardrop is re-asserted, at which point it will disappear as a potential destination and a different illegitimate destination in the reverse direction may be the nearest apparent destination. In that case, re-negating the precipitant will make the original illegitimate destination appear to be nearest again, causing the direction of motion to reverse again ad infinitum.
[0280] In order to prevent infinite dithering from happening when a Nearest Destination method is being used, any of the following strategies may be used: (1) explicitly indicating pseudo-assumptions that are illegitimate destinations, populating this indication at the time of making the counter-assertion that negates the precipitant for best efficiency, and allowing this indication to be recessively inherited by assertions that are led to and produced by the counter-assertion that identifies the teardrop in context, or (2) regularly comparing the value predicates for the same variable that are in the full reasons to re-identify when apparent pseudo-assumptions are not legitimate destinations, or (3) making a similar re-identification while back-tracking, or (4) modifying the method by adding a rule that the contradiction should not reverse direction unless all other possible directions of motion are restricted and those restrictions are fully supported by unconditional assertions, producing a method called Nearest Destination Ahead.
[0281] An explicit indication of an illegitimate destination is effectively a declaration that the pseudo-assumption will have a valid reason at any time when it is possible to counter-assert the term restricted by that value predicate within the currently recorded prevailing path and therefore it should not be treated as not having a valid reason even though a valid reason is not currently recorded. As mentioned, the heritability of an explicit indication of an illegitimate destination should be recessive, meaning that if a first prevailing path has such an indication and a second prevailing path that is disjunctively converging or conjunctively converging with the first prevailing path does not have such an indication then the result should have no such indication. The nearness count for an illegitimate destination should similarly be propagated recessively. Because the same term may appear to be an illegitimate destination in one sub-path and simultaneously appear to be a legitimate destination in another sub-path, when using back-tracking to identify destinations it is necessary to keep a record of all values encountered during the search, which is best embodied by a history of elements that have been popped from the stack.
[0282] The possibility of dithering is the main reason that it is best for prevailing assertions to persist, especially so when full reasons are not being used and it is necessary to back-track in order to obtain the information that Behavior #2 relies upon.
[0283] A method that moves a contradiction toward the nearest destination regardless of whether it is ahead or behind the most recent counter-assertion is called the Strictly Nearest Destination method. A method that moves a contradiction in the direction in which a preferred destination appears nearest is called the Nearest Preferred Destination method, and there is also a Nearest Preferred Destination Ahead method. Each of the methods listed are members of the class of Nearest Destination methods.
[0284] Farthest Reversal
[0285] Another class of methods that enables Behavior #4 to be exhibited when Behaviors #1 and #3 have already been enabled to be exhibited is called the “Farthest Reversal” method. Farthest Reversal relies upon differentiating the paths that lead to the prevailing conditional assertions that restrict terms in the contradicted constraint.
[0286] The construction of the compressed full reason effectively employs cascading branch-subtractions. This same method of cascading branch-subtractions can be used to differentiate full reasons. Specifically, the final co-basis before it is added to the basis is a “differentiated reason” relative to the basis.
[0287] In a Farthest Reversal method, it is necessary to identify the term in a constraint that was most recently conditionally restricted. This identification may be facilitated by recording the order in which all terms of a constraint are restricted. Such an ordering may be recorded for each constraint individually, or prevalence numbers may be used for this purpose.
[0288] The Full Farthest Reversal method may include the following operations:
[0289] [F1] A destination is chosen for the motion of a given contradiction. The manner of choosing is not important as long as the choice is legitimate and persistent. If it is revealed that the chosen destination is not in the paths that lead to the given contradiction, then another destination is chosen; but otherwise, the choice should persist as the contradiction moves through the constraints.
[0290] [F2] If only one or two terms in the given contradicted constraint are restricted by a determinant that has the destination in the full reasons of the prevailing assertions that conjunctively converge into it:
[F2a] The term that is the least recently restricted term among such similarly qualified terms is the term for which a value predicate is to be counter-asserted.
[0292] [F3] Otherwise:
[F3a] Among terms in the given contradicted constraint that are restricted by a determinant that has the destination in the full reasons of the prevailing assertions that conjunctively converge into it, the term that was most recently restricted is designated as the “main” term and the prevailing path of the main term is the “main path”. [F3b] For each term in the given contradicted constraint that is restricted by a determinant that has the destination in the full reasons of the prevailing assertions that conjunctively converge into the determinant:
[F3b1] Initialize a “pruned co-basis” as empty for the given term. [F3b2] For each prevailing assertion that conjunctively converges to produce the determinant that restricts the given term and that has the destination in its full reason:
[F3b2a] Copy the full reason of the given prevailing assertion as the “temporary co-basis”. [F3b2b] For each value predicate in the temporary co-basis that does not represent the destination or the value predicate of a prevailing assertion that has a full reason that contains the destination, in ascending order of farness counts:
[F3b2b1] Branch-subtract the prevailing assertion that represents the given value predicate from the temporary co-basis, and remove the given value predicate from the temporary co-basis.
[F3b2c] Branch-add the temporary co-basis to the pruned co-basis, and add the value predicate of the given prevailing assertion to the pruned co-basis for the given term.
[F3c] Copy the pruned co-basis for the main term as the “main basis”, and eliminate the pruned co-basis for the main term. [F3d] For each term in the given contradicted constraint that has a remaining pruned co-basis:
[F3d1] For each value predicate in the pruned co-basis of the given term, in ascending order of farness counts:
[F3d2a] If the given value predicate is in the main basis of the given term, then branch-subtract the prevailing assertion of the given value predicate from the pruned co-basis of the given term.
[F3e] The term in the given contradicted constraint that has a remaining pruned co-basis that contains a value predicate with the greatest farness count is the term to be counter-asserted.
[0306] In a Farthest Reversal method, as in Nearest Destination methods, if the counts are not maintained rigorously, the motion of contradictions may dither. In both methods, the number of dithers is limited by the number of constraints that may be contradicted or may provide an impetus for a change of direction of motion of an existing contradiction, and the maximum number of times a single constraint may be traversed by a contradiction in response to a dither is equal to the number of terms in that constraint, and a new set of dithers is possible whenever an assumption is introduced. Any method of choosing a direction in which to move a contradiction that limits the number of constraint traversals per dither to the number of terms in the constraint and limits the number of dithers per assumption to the number of constraints in the expression is an acceptable method.
[0307] A Farthest Reversal method works by consistently choosing a path that does not join the main path or joins the main path at the farthest possible point from the contradiction relative to distance as measured in the main path itself, and this prevents the motion of the contradiction from doubling-back on the main path and then redoubling-back except in cases where information about the path is lost or not previously available.
[0308] There are a number of varieties of Nearest Destination methods; and similarly, there are a number of varieties of Farthest Reversal methods. However, while Nearest Destination methods may vary according to how nearness is measured, applying different ways of measuring farness to Farthest Reversal methods produces orderings of assertions in a prevailing path that are similar to one another. A more substantial example of a variant of a Farthest Reversal method is one that uses stratified reasons.
[0309] Stratified Reasons
[0310] A “stratified reason” is a kind of record of a prevailing path that is limited to constraints that provide prevailing assertions that have a specific assumption in their prevailing paths. These constraints are stratified in the sense that every constraint that produces an assertion as a result of the introduction of a first assumption may be a part of the stratified reason of another constraint in that same set, and every constraint that produces an assertion as a result of the introduction of the first assumption in combination with a second assumption may be a part of the stratified reason of another constraint in this latter set, and thus the constraints are separated into “strata” with each stratum being assigned to a specific latest assumption that is called the “source” for the assertions in its stratum. A stratified reason is similar to a pruned co-basis as is described above, except that a pruned co-basis does not contain value predicates that represent restrictions from other strata and does not include paths that lead to pseudo-assumptions without also leading to the specified assumption through the same constraints, and except that stratified reasons do not have fulfilled counts, unfulfilled counts, or nearness counts but do contain prevalence numbers but the prevalence numbers are not revised to serve as rigorously maintained farness counts. As such, stratified reasons are part of the prior are where they are simply called “reasons”.
[0311] Being similar to a pruned co-basis is the chief advantage of using stratified reasons as part of an embodiment that use a Farthest Reversal method, because it reduces the cost of producing an actual pruned co-basis. However, when a first rhizomatic network shrinks because portions of it are being consumed by a second rhizomatic network of a different stratum, the paths of the first rhizomatic network that lead to and produce restrictions in the prevailing path of the second rhizomatic network are not available; and consequently, the motion of contradictions in the second rhizomatic network will not recognize that counter-assertions should be unconditional without the occurrence of dithering down those other paths of the first rhizomatic network. In addition, prevalence numbers that are not rigorously maintained as farness counts will cause additional dithering, and rigorous maintenance is itself additional computational work. So altogether a variant of Farthest Reversal methods that uses stratified reasons will not be especially efficient.
[0312] Variants of Farthest Reversal methods may provide small reductions to the computational costs by finding a shorter path to the point of rejoining the main path or by preferring to choose a destination for which a short path to the point of rejoining the main path exists.
[0313] Because Nearest Destination methods require traveling minimum distances or traveling a path that is expected to incur minimal computational costs to expel a contradiction, and the Farthest Reversal method requires traveling to a point that is earliest in the main path, regardless of the distance traveled or computational cost of traversing that distance, Nearest Destination methods will tend to incur lesser computational costs in order to expel a contradiction, providing Nearest Destination methods with advantages over certain alternatives.
[0314] Adjusting the Methods that Enable an Algorithm to Exhibit Behavior #4
[0315] In some cases it is possible that a contradiction must be moved in a direction different from the direction that would be chosen according to Nearest Destination or Farthest Reversal. This may be the case when the complement of a counter-assertion would have been empty or a system of SOMMEs requires that only certain variables may have value predicates counter-asserted. When this is the case, it is necessary to adjust the method of choosing a direction, whether that method is Nearest Destination or Farthest Reversal. One way to provide this adjustment is to associate the desired term to be counter-asserted, identified by the value predicate found in the full reason that restricts that term, with the contradiction in motion, efficiently embodied as a data structure associated with the process of resolving contradictions, rather than being associated with a variable, constraint, term, or assertion. More than one such process notation may be necessary per process, but the number of such notations cannot exceed the number of variables in the expression.
[0316] Some descriptions above of methods that are used to choose a direction in which to move a contradiction are written as if a destination has been pre-chosen. In cases where there is no prescribed preference for negating certain assumptions rather than other assumptions, it is often useful to modify the methods for choosing a direction by subtracting the conditional prevailing assertions that restrict other terms in the contradicted constraint from the prevailing path of each term that is a candidate for counter-assertion. Doing this has the effect of limiting the decisive information for each candidate term to those factors that are not derived solely from paths that pass through the other candidate terms.
Other Embodiments of the Present Invention
[0317] When there are user preferences that certain variables obtain specific values and the algorithm is altered to respect those preferences, then the alteration embodies a “conservative” variant of the algorithm. When no alteration is implemented, a “dynamic” variant of the algorithm is embodied.
[0318] When multiple preferences have identical rank, it is possible to embody the difference as a preference for certain destinations when resolving a contradiction. However, when rigorous optimization is required, it is necessary to embody the present invention as a process that finds a satisfying value assignment for the variables, followed by another process that takes the resulting network, including reasons, and imposes, one-at-a-time in ranked order of preference, the preferred values as unconditional assertions, rejecting any such unconditional assertion if it produces a necessary contradiction.
[0319] Complex preference structures may be embodied as additional constraints, such as constraints that may be interpreted as representing the sum, product, or other result of an optimization scoring regimen. In this case, the preferences are imposed on the variables that represent this result.
[0320] Embodiments of the present invention may be implemented in various ways. The choice of implementation for a particular substrate may depend on the implementational economies available to that substrate. Specifically, the production of devices typically trades a linear increase in computational time in order to save a squared cost of space for mechanisms, and the production of software often makes the opposite trade preferring to save computational time at the expense of additional memory usage. One particular useful embodiment of the present invention, which provides a low maximum computational cost, embodies a single-threaded dynamic variant that performs a Nearest Destination method of choosing a direction in which to move contradictions and stores compressed full reasons that include unfulfilled counts and maximum distance counts and restriction counts. The majority of the full reasons are best maintained rigorously, but the maximum distance counts and restriction counts are best maintained lazily, and SOMME value predicate revisions are best maintained lazily unless the present invention is supplemented by a process that provides conventional mathematical analysis.
[0321] Generality
[0322] Embodiments of the present invention use relationships between the constraints themselves to define the proximal space through which contradictions move. Consequently, the motion of contradictions is not affected by the nature of the values, whether they are well-ordered, partially-ordered, or disjoint, and whether they are mutually-exclusive or fuzzy; nor is this motion affected by the quality of the value predicates, whether they are intervals, sets, or discrete values; nor is this motion affected by the quality or shape of the extension of the constraints, whether it is continuous, bifurcated, or discrete, and whether it is convex, contiguous but non-convex, or non-contiguous, or there is no feasible extension at all. Neither is the correctness of embodiments of the present invention nor the order of magnitude of the maximum computational expenditure adversely affected by the order in which assumptions are made or the order that determines which assertion among competing assertions becomes prevailing. However, the maximum computational expenditure of embodiments of the present invention is affected by the number of variables, the number of differentiated values of those variables, and the number of constraints; and because SOMMEs may operate on variables with an infinite number of values, the motion and maximum computational expenditure of embodiments of the present invention is affected by whether the constraints are disjunct phrases or other explicitly logical expressions or SOMMEs.
[0323] The number, direction, and conditionality of counter-assertions resulting from the resolution of a contradiction when the expression includes SOMMEs may be different than when the expression contains only disjunct phrases, as was mentioned above; but the definition of proximity of constraints and the proximal space that the constraints define and through which the contradictions move remains unaffected. Consequently, embodiments of the present invention provide a means of processing expressions that is much more versatile than methods that rely on linear expressions, Euclidean distance, conventional topological nearness, or a convex extension.
EXAMPLE EMBODIMENTS
Embodiment #1
General Computation
[0324] One embodiment of the present invention is a general improvement to computerized computation, providing a reduction in the costs of running the computational device while solving a problem in NP, NP-complete, or NP-hard, and a reduction in the amount of time that an operator of the computational device must wait for a result while solving a problem in NP, NP-complete, or NP-hard. This embodiment of the present invention is comparable to a new arithmetic circuit in a calculator or to a software module that emulates such a circuit.
Embodiment #2
Template Making
[0325] One embodiment of the present invention is a device or automated process that renders templates that are used by another machine to cut parts from material or otherwise used by a machine to guide some processing of material into components of a product, whether the process is producing lumber from timber, clothing panels from cloth, leather, or plastic, or car or other machine parts from metal sheets, bars, or wire, or some other manufactured part from a refined material.
[0326] The technical effect of this embodiment is that templates are provided that permit optimal utilization of materials without excessive computational costs, which reduces waste of both material and computational costs. This optimization typically uses variables and constraints that represent the geometric requirements of the parts to be rendered and may also include constraints that reflect the different economic values of parts that might be rendered from a particular piece of stock, as well as including constraints that summarize the utilization of materials and value of the product in order that a conservative variant of this embodiment of the present invention may force the production of a template that maximizes the utilization of stock or value produced. When the constraints reflect the different values of parts, then an additional technical effect is the maximization of the value of the product.
[0327] (See Javanshir, H. and Shadalooee, M. “The Trim Loss Concentration in One-Dimensional Cutting Stock Problem (1D-CSP) by Defining a Virtual Cost” Journal of Industrial Engineering International 2007;
[0000] Kenyon, Claire and Rémila, Eric “A Near-Optimal Solution to a Two-Dimensional Cutting Stock problem” Mathematics of Operational Research 2000.)
Embodiment #3
Cutting Machine Control
[0328] One embodiment of the present invention is a part of the control mechanism of a cutting machine, drilling machine, grinding machine, or other machine that renders parts from stock material, whether the process being supplied by the machine is cutting lumber from timber, furniture parts from lumber, panels from cloth, leather, or plastic, or car or other machine parts from metal sheets, bars, or wire, or some other manufactured part from a refined material.
[0329] The technical effect of this embodiment is the control of the drills or cutting surfaces that provide optimal utilization of materials without excessive computational costs, which reduces waste of material, computational costs, and total cutting time. This optimization typically uses variables and constraints that represent geometric requirements of the parts that are being rendered and may also include constraints that represent the different economic values of parts that might be rendered from a particular piece of stock, as well as including constraints that summarize the utilization of materials and value of the product in order that a conservative variant of this embodiment of the present invention may force a rendering of parts that maximizes the utilization of stock or value produced. When the constraints reflect the different values of parts, then an additional technical effect is the maximization of the value of the product.
[0330] (See Javanshir and Shadalooee op. cit.; Kenyon and Rémila op. cit.)
Embodiment #4
Robotic Vehicle Control
[0331] One embodiment of the present invention is a part of the control mechanism of a robotic vehicle, allowing the vehicle to choose expedient paths to its destinations.
[0332] The technical effect of this embodiment is a minimization of travel time or cost, while reducing wait-times and computational costs associated with making the decisions that drive the vehicle. This minimization typically uses variables and constraints that represent the geographic locations of destinations, the geographic paths between various positions, and physical or economic impediments associated with the various path segments, in addition to constraints that summarize the physical and economic impediments in order that a conservative variant of this embodiment of the present invention may force the choice of a path with a minimal travel time or cost.
[0333] (See Peng, Jufeng and Akella, Srinivas “Coordinating Multiple Robots with Kinodynamic Constraints along Specified Paths” International Journal of Robotics Research 2005.)
Embodiment #5
Data Compression
[0334] One embodiment of the present invention is a device or automated process that compresses data, whether the data represents text, an image, an audio message, a video recording, an executable binary, or some other encrypted or non-encrypted unit of information, whether the data is digital or can be represented as a Fourier decomposition or other algebraic decomposition of analog data.
[0335] The technical effect of this embodiment is an optimization of the compression effect on a unit of information relative to the costs of computations that produce the compression. This optimization typically uses variables and constraints that represent preferences about the elapsed time required to decompress the information and constraints that reflect computational costs and compressive benefits of various strategies for compression, in addition to constraints that represent a summarization of compression in order that a conservative variant of this embodiment of the present invention may force an optimally compressed result.
[0336] (See Ruhl, Matthias and Hartenstein, Hannes “Optimal Fractal Coding is NP-Hard” Proceedings of the International Conference on Image Processing 1997.)
Embodiment #6
Protein Design
[0337] One embodiment of the present invention is a device or automated process that provides a sequence of amino acids that conforms to a given geometric structure.
[0338] The technical effect of this embodiment is a reduction of the time and computational expense associated with the production of custom proteins or models of custom proteins and a reduction in the wait-time for designers. Such a device or automated process typically uses variables and constraints that represent the chemical limitations on amino acid positioning in a peptide, whether those limitations are based on hydrogen bonding, ionic interactions, Van der Waals forces, or hydrophobic packing, or other known or suspected chemical properties or environmental conditions, in addition to constraints that reflect the preferred three-dimensional shape of the protein in order that a dynamic variant of this embodiment of the present invention may produce a conforming sequence of amino acids.
[0339] (See Pierce, Niles A. and Winfree, Erik “Protein Design is NP-Hard” Protein Engineering 2002.)
Embodiment #7
Telecom Traffic Routing
[0340] One embodiment of the present invention is a device or automated process that optimizes the utility of a telecom network relative to cost by routing messages away from network congestion.
[0341] The technical effect of this embodiment is the optimization of the utility of the message routing capability of an existing telecom network while reducing wait-times and saving computational costs associated with providing that utility. This optimization typically uses variables and constraints that represent the topology of the telecom network, measurements of congestion on the network, the utilitarian values of messages to be transmitted, and various costs of using and transmission speeds across various segments of the network, in addition to using constraints that summarize the costs and utility in order that a conservative variant of this embodiment of the present invention may force an optimal routing for the message load.
[0342] (See Gibbens, R. J. et al. “Dynamic Alternative Routing—Modelling and Behaviour” Proceedings of the 12 th International Teletraffic Congress 1988.)
Embodiment #8
Wavelength Division Multicasting Traffic Grooming
[0343] One embodiment of the present invention is a device or automated process that produces an ADM installation plan consisting of a list of wavelengths and a number of add-drop multiplexors (ADMs) per fiber that is optimal with respect to hardware cost or blocking probability.
[0344] The technical effect of this embodiment is the optimization of the WDM network to minimize the costs of constructing and maintaining the network or the probability of reaching a traffic-blocking condition, while saving computational costs associated with performing the optimization that results in the production of the list of wavelengths and number of ADMs. This optimization typically uses variables and constraints that represent the available bandwidth of the transmission channel, the costs of optics, ADMs, and other components of the network, and possibly expected traffic demands, in addition to constraints that summarize the costs or blocking probability so that a conservative variant of this embodiment of the present invention may force an ADM installation plan that minimizes costs or blocking probability.
[0345] (See Capone, Antonio et al. “Multi-layer Network Design with Multicast Traffic and Statistical Multiplexing” Global Telecommunications Conference 2007.)
Embodiment #9
Satellite Placement
[0346] One embodiment of the present invention is a device or automated process that produces a placement specification for a set of orbital satellites that satisfies service arc requirements while minimizing the likelihood of communications interference and collision.
[0347] The technical effect of this embodiment is an optimization of the placement of satellites that provides a minimized cost composed of a combination of risk of destruction and degradation of service caused by communication interference, while saving computational costs associated with performing the optimization. This optimization typically uses variables and constraints that represent orbital mechanics, the shell in which the set of satellites may be placed, the orbits of existing satellites and debris, the positions of base stations and other surface objects that define the value of the service arcs of each of the satellites, and the positioning costs for various locations in the shell, in addition to constraints that summarize the values and costs of the placement specification so that a conservative variant of this embodiment of the present invention may force the production of an optimal placement specification.
[0348] (See Spälti, Susan B. and Liebling, Thomas M. “Modeling the satellite placement problem as a network flow problem with one side constraint” Operations Research Spektrum 1991.)
Embodiment #10
Component Design
[0349] One embodiment of the present invention is a device or automated process that produces a component design that minimizes the cost of labor and materials required to manufacture components that meet required physical specifications, whether those components are structural trusses, submarine propellers, electrical batteries, or any other kind of component.
[0350] The technical effect of this embodiment is the minimization of manufacturing costs of physical components, while saving computational costs associated with producing such a minimization and while saving the wait-time of component designers. This minimization typically uses variables and constraints that represent the specifications of the physical requirements of the components, the available materials that may be used to construct the component and their stock specifications, the relationships that determine how the types of materials and their configuration affect the physical properties of the component, and the costs of altering stock material into parts and assembling them, in addition to constraints that summarize the costs in order that a conservative variant of this embodiment of the present invention may force a design that minimizes the manufacturing costs.
[0351] (See Pownuk, Andrzej “Optimization of mechanical structures using interval analysis” Computer Assisted Mechanics and Engineering Sciences 2000.)
Embodiment #11
Cryptanalysis
[0352] One embodiment of the present invention is a device or automated process that finds multiplicative factors or inverts hashes that have been used to encrypt data.
[0353] The technical effect of this embodiment is the decomposition of a cypher-text into a plain-text, while saving computational costs associated with producing this decomposition. Such a device or automated process typically uses variables and constraints that represent the cypher-text as well as representing known or suspected encryption algorithms that have been or may have been applied to the plain-text in order to produce the cypher-text in order that a dynamic variant of this embodiment of the present invention may produce clear-text.
[0354] (See Valée, Brigitte “Generation of Elements with Small Modular Squares and Provably Fast Integer Factoring Algorithms” Mathematics of Computation 1991.)
Embodiment #12
CPU Job Scheduling
[0355] One embodiment of the present invention is a device or automated process that produces a schedule of jobs to be processed by a computer's central processing unit (CPU) that maximizes the throughput or responsiveness of the CPU under a given workload or minimizes the energy usage.
[0356] The technical effect of this embodiment is the maximization of throughput or responsiveness of the CPU or minimization of the energy usage, while saving computational costs associated with producing the schedule, which in turn provides an additional improvement to the throughput or responsiveness of the CPU. Such a device or automated process typically uses variables and constraints that represent the jobs to be executed and their urgency, the sub-steps of the jobs and their order, the resources required for each sub-step, and the resources available to the CPU, in addition to constraints that summarize the energy used or measurements that reflect the responsiveness or throughput of the CPU when executing the schedule of jobs so that a conservative variant of this embodiment of the present invention may force a maximization of throughput or responsiveness or a minimizations of energy use.
[0357] (See Baruah, Sanjoy K. “Preemptively Scheduling Hard-Real-Time Sporadic Tasks on One Processor” Real - Time Systems Symposium 1990.)
Embodiment #13
IC Test Bus Development
[0358] One embodiment of the present invention is a device or automated process that produces a design for an on-chip test access architecture or test access mechanism (TAM) for a system-on-chip (SOC) or other complex integrated-circuit chip (IC) that includes a test bus, where this design includes an assignment of cores to test buses, the widths of the test buses and their subdivisions, and a schedule of tests.
[0359] The technical effect of this embodiment is an optimization of the test bus that provides a maximization of the testing utility value relative to the construction costs of the test bus, while saving computational costs associated with performing the optimization. This optimization typically uses variables and constraints that represent the cores and their input pins, the various tests required and their core pin access requirements, the times to complete the various tests, the value of reduced testing time, and the costs of increasing test bus widths, in addition to constraints that summarize the value of testing time required by the schedule of tests and the costs of constructing the buses in order that a conservative variant of this embodiment of the present invention may force an optimization of the testing utility value relative to the construction costs of the test bus.
[0360] (See Chakrabarty, Krishnendu “Optimal Test Access Architectures for System-on-a-Chip” ACM Transactions on Design Automation of Electronic Systems 2001.)
Embodiment #14
IC Circuit Partitioning, Floorplanning, & Placement
[0361] One embodiment of the present invention is a device or automated process that produces a circuit layout that separates a logically-defined complex behavior into multiple modules, circuit cores, cells, or blocks suitable for positioning as part of an IC, where the layout satisfies size limitations or limitations on the number or size of interconnects between the circuit cores, cells, or blocks that in turn may provide a circuit delay that is within desired limits.
[0362] The technical effect of this embodiment is a partitioning of the circuit that satisfies the size and circuit delay limitations, while saving computational costs associated with producing the circuit layout. Such a device or automated process typically uses variables and constraints that represent the logical behavior of the circuit, the possible translations of individual logical behaviors into sub-circuits, the sizes and circuit delays of the various sub-circuits, including limitations on juxtaposition of various sub-circuit components caused by the geometry of the chip and various electrical effects, the limitations on the partition sizes and circuit delays, and a summarization of the sizes and delays of the circuit layout in order that a dynamic variant of this embodiment of the present invention may produce a satisfying layout. The constraints used by such a device or automated process may also represent costs of construction and a formula that provides a trade-off between costs and performances in order that a conservative variant of this embodiment of the present invention may force a circuit layout that provides an optimization of the trade-off.
[0363] (See Kahng, Andrew B. et al. VLSI Physical Design: from Graph Partitioning to Timing Closure 2011.)
Embodiment #15
IC Power, Ground, Clock, & Netlist Routing
[0364] One embodiment of the present invention is a device or automated process that produces a wiring plan for an IC, whether that plan includes routing for power pins, ground pins, clock signal pins, or connecting input and output pins for the various cores, cells, or blocks of the IC, where the plan satisfies limitations on the length and width of interconnects between the cores, cells, or blocks so that the interconnects do not exceed the available space on the IC and circuit delay limitations for the IC are not violated.
[0365] The technical effect of this embodiment is the production of a wiring plan that satisfies size and circuit delay limitations, while saving computational costs associated with producing the wiring plan. Such a device or automated process typically uses variables and constraints that represent the various cores, cells, or blocks and their shapes and pins, the list of connections between the output pins of each core, cell, or block to the required input pins on other cores, cells, or blocks, the list of connections of chip input pins to core, cell, or block input pins, limitations on the sizes of interconnects that are due to the geometry of the chip size and fabrication processes, limitations on juxtaposition of interconnects that are due to electrical effects such as capacitive coupling or inductive cross-talk, and the possibility of implementing clock closure techniques such as extra-wide interconnects and cloning modules, in addition to constraints that summarize the space consumed by the cores, cells, or blocks and possibly the signal delay of clock circuits in order that a dynamic variant of the present invention may force a wiring plan that satisfies the space and signal delay requirements. The constraints typically used by such a device or automated process may also represent costs of construction and a formula that provides a trade-off between cost and performance in order that a conservative variant of this embodiment of the present invention may force a wiring plan that provides an optimal balance between cost and performance.
[0366] (See Kahng, Andrew B. et al. op. cit.)
Embodiment #16
Advanced IC Fabrication
[0367] One embodiment of the present invention is a device or automated process that produces masks for IC fabrication that satisfy size and performance requirements and a list of fabrication process that should be applied in combination with the masks in order to directly produce an IC that satisfies behavioral specifications.
[0368] The technical effect of this embodiment is a greatly streamlined IC design process that, while theoretically possible without the present invention, only becomes practical because of the computational cost savings provided by the present invention. Such a device or automated process typically uses variables and constraints that represent all the technical limitations of IC fabrication in general, the specific limitations of the proposed fabrication facility, geometrical limitations of the various wafer sizes on which the IC may be created, coding requirements for producing the masks themselves, whether the masks are for deposition, removal, patterning, or modification of electrical properties, the desired functional behavior of the IC, required tests for the IC behavior, various implementations of components that provide identical functional behavior but differ in their electrical, magnetic, or signal propagation properties, in addition to constraints that summarize the size and performance characteristics of the IC in order that a dynamic variant of the present invention may force the production of masks and process applications that satisfy the behavioral, size, and performance requirements. The variables and constraints used by such a device or automated process may also represent the costs of the various component implementations, the expected value and market demand of the IC for various size and performance ranges, costs of new IC fabrication start-up, in addition to constraints that summarize the costs and market value of an IC design in order that a conservative variant of this embodiment of the present invention may force the production of masks and process applications that optimize the cost of the IC relative to expected market value and demand.
Embodiment #17
Control System Design
[0369] One embodiment of the present invention is a device or automated process that produces a design of a control system, such as a nuclear reactor control system, or a control system for a forge, or any other system that controls a complex process.
[0370] The technical effect of this embodiment is the production of an optimal design, while saving computational costs associated with producing the optimization and while saving the wait-time of designers. This optimization typically uses variables and constraints that represent the available control elements, including their costs and effects, and a characterization of the control problem, including acceptable tolerances for the precision of control, in addition to constraints that summarize the cost or the precision in order that a conservative variant of this embodiment of the present invention may force a design that is optimized for cost or precision.
[0371] (See Blondel, Vincent D. and Megretski, Alexandre eds. Unsolved Problems in Mathematical Systems and Control Theory 2009.)
Embodiment #18
Robotic Inverse Kinematics
[0372] One embodiment of the present invention is a device or automated process that produces a set of instructions that guide the movement of a robot so that it achieves a specified position while traversing a field of obstacles.
[0373] The technical effect of this embodiment is the production of the set of robotic instructions, while saving computational costs associated with producing the set of instructions and while reducing the time to bring the instructions to production. Such a device or automated process typically uses variables and constraints that represent the desired destination position, the dimensions and positions of obstacles to be avoided, the dimensions and starting position of the robot, the possible motions of the robot, including the resultant change in position or dimensions of the robot and the cost of each motion, in addition to constraints that summarize the cost of the motion in order that a conservative variant of this embodiment of the present invention may force a set of instructions that result in motions that achieve the desired destination position with the least cost.
[0374] (See Parsons, David and Canny, John “Geometric Problems in Molecular Biology and Robotics” ISMB 1994.)
Embodiment #19
Optimizing Compiler
[0375] One embodiment of the present invention is a device or automated process that compiles software source code into machine code, whether the support is for register allocation, instruction selection, macro compression, loop optimization, data layout optimization, code parallelization, or any other complex compilation process.
[0376] The technical effect of this embodiment is the production of aggressively optimized machine code, while saving computational costs associated with the optimization and while saving the wait-time of code developers. This optimization typically uses variables and constraints that represent the source code, the available registers, including their sizes, the available operations, including their computational costs and any specific register assignments, the available spill resources, including their sizes and computational costs of access, and tilings that map source code instructions to sets of machine instructions, in addition to constraints that summarize the computational costs in order that a conservative variant of this embodiment of the present invention may force the production of machine code that satisfies the source code and has minimal computational costs.
[0377] (See Kremer, Ulrich “Optimal and Near-Optimal Solutions for Hard Compilation Problems” Parallel Processing Letters 1997;
[0000] Megiddo, Nimrod and Sarkar, Vivek “Optimal Weighted Loop Fusion for Parallel Programs” Proceedings of the ninth annual ACM symposium on Parallel algorithms and architectures 1997.)
[0378] Referring to FIG. 2 , a flowchart is shown of a method 200 performed by a computer system implemented according to one embodiment of the present invention. The method 200 moves contradictions through a proximal space defined by a rhizomatic network that consists of prevailing paths of implication responsive to counter-asserting value predicates ( FIG. 2 , operation 202 ). The counter-assertions are assertions of value predicates that negate other assertions, which causes the prevailing paths of negated assertions to be moved from the prevailing paths of remaining assertions. The remaining assertions include the counter-assertions.
[0379] The method 200 also produces counter-asserted value predicates that do not create a contradiction in any constraint that remains in the prevailing path of the counter-assertion ( FIG. 2 , operation 204 ). The method 200 also collects first data representing the prevailing paths of implication and the prevailing paths of motion of contradictions ( FIG. 2 , operation 206 ). The method 1700 also uses the first data to inform choices of direction so that contradictions move toward locations in the proximal space where no validly reasoned disagreement is recorded ( FIG. 2 , operation 208 ). The method 200 also chooses contradictions to be resolved and terms to be counter-asserted in a way that excludes dithering ( FIG. 2 , operation 210 ).
[0380] It is to be understood that although the invention has been described above in terms of particular embodiments, the foregoing embodiments are provided as illustrative only, and do not limit or define the scope of the invention. Various other embodiments, including but not limited to the following, are also within the scope of the claims. For example, elements and components described herein may be further divided into additional components or joined together to form fewer components for performing the same functions.
[0381] Any of the functions disclosed herein may be implemented using means for performing those functions. Such means include, but are not limited to, any of the components disclosed herein, such as the computer-related components described below.
[0382] The techniques described above may be implemented, for example, in hardware, one or more computer programs tangibly stored on one or more computer-readable media, firmware, or any combination thereof. The techniques described above may be implemented in one or more computer programs executing on (or executable by) a programmable computer including any combination of any number of the following: a processor, a storage medium readable and/or writable by the processor (including, for example, volatile and non-volatile memory and/or storage elements), an input device, and an output device. Program code may be applied to input entered using the input device to perform the functions described and to generate output using the output device.
[0383] Each computer program within the scope of the claims below may be implemented in any programming language, such as assembly language, machine language, a high-level procedural programming language, or an object-oriented programming language. The programming language may, for example, be a compiled or interpreted programming language.
[0384] Each such computer program may be implemented in a computer program product tangibly embodied in a machine-readable storage device for execution by a computer processor. Method steps of the invention may be performed by one or more computer processors executing a program tangibly embodied on a computer-readable medium to perform functions of the invention by operating on input and generating output. Suitable processors include, by way of example, both general and special purpose microprocessors. Generally, the processor receives (reads) instructions and data from a memory (such as a read-only memory and/or a random access memory) and writes (stores) instructions and data to the memory. Storage devices suitable for tangibly embodying computer program instructions and data include, for example, all forms of non-volatile memory, such as semiconductor memory devices, including EPROM, EEPROM, and flash memory devices; magnetic disks such as internal hard disks and removable disks; magneto-optical disks; and CD-ROMs. Any of the foregoing may be supplemented by, or incorporated in, specially-designed ASICs (application-specific integrated circuits) or FPGAs (Field-Programmable Gate Arrays). A computer can generally also receive (read) programs and data from, and write (store) programs and data to, a non-transitory computer-readable storage medium such as an internal disk (not shown) or a removable disk. These elements will also be found in a conventional desktop or workstation computer as well as other computers suitable for executing computer programs implementing the methods described herein, which may be used in conjunction with any digital print engine or marking engine, display monitor, or other raster output device capable of producing color or gray scale pixels on paper, film, display screen, or other output medium.
[0385] Any data disclosed herein may be implemented, for example, in one or more data structures tangibly stored on a non-transitory computer-readable medium. Embodiments of the invention may store such data in such data structure(s) and read such data from such data structure(s).
[0386] Although certain embodiments may be described herein using language that may be similar to language that may be used to describe mental acts, such as “decide,” “analyze,” and “conclude,” such language is used merely for convenience and as a shorthand to describe physical acts that are performed by embodiments of the present invention using physical components, such as transistors, logic gates, and processors. Such language, therefore, should be interpreted solely to refer to such physical acts performed by physical components, and not to any mental acts performed by the mind of a person or any other living being.
[0387] Similarly, although certain embodiments may be described herein using mathematical and philosophical language, such as “contradiction,” “variable,” and “constraint,” such language is used merely for convenience and as a shorthand to describe concrete physical properties of physical components and physical acts that are performed by such components, and not to any abstract ideas, whether mathematical, philosophical, or otherwise. Such language, therefore, should be interpreted solely to refer to such physical properties of physical components and to physical acts performed by such components, and not to any abstract ideas, whether mathematical, philosophical, or otherwise.
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Within satisfaction problems or any decision or other problem which is reducible to a satisfaction problem, the invention tracks the paths along which implications propagate and identifies conditional contradictions and subsequently moves the contradictions back down the implicational paths toward assumptions or other unreasoned assertions in order to expel the contradictions. The action is completed in less time than is incurred by existing methods and thus provides a performance improvement to the devices, software, or processes which address such problems. Such problems are addressed by devices, software, and processes related to many technical fields, including: ore refining; pipeline routing; yarn manufacture; fabric cutting; sawyering; mechanical component design; structural design of data processing systems; design and analysis of circuits or semiconductor masks; inspection and guarding of containers, pipes, and galleries; sensor array operations; orbital satellite operations; data compression; chemical analysis; design and analysis of proteins.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U. S. Provisional Application No. 60/633,190 “Visual Prosthesis for Improved Circadian Rhythms”, filed Dec. 3, 2004, the disclosure of which is incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This invention was made with government support under grant No. R24EY12893-01, which has been awarded by the National Institutes of Health. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION
Field of the Invention
[0003] The present invention is generally directed to neural stimulation and more specifically to neural stimulation of the visual system for improved circadian rhythms and a method of improving the circadian rhythms.
Background of the Invention
[0004] In 1755 LeRoy passed the discharge of a Leyden jar through the orbit of a man who was blind from cataract and the patient saw “flames passing rapidly downwards.” Ever since, there has been a fascination with electrically elicited visual perception. The general concept of electrical stimulation of retinal cells to produce these flashes of light or phosphenes has been known for quite some time. Based on these general principles, some early attempts at devising prosthesis for aiding the visually impaired have included attaching electrodes to the head or eyelids of patients. While some of these early attempts met with some limited success, these early prosthetic devices were large, bulky and could not produce adequate simulated vision to truly aid the visually impaired.
[0005] In the early 1930's, Foerster investigated the effect of electrically stimulating the exposed occipital pole of one cerebral hemisphere. He found that, when a point at the extreme occipital pole was stimulated, the patient perceived a small spot of light directly in front and motionless (a phosphene). Subsequently, Brindley and Lewin (1968) thoroughly studied electrical stimulation of the human occipital (visual) cortex. By varying the stimulation parameters, these investigators described in detail the location of the phosphenes produced relative to the specific region of the occipital cortex stimulated. These experiments demonstrated: (1) the consistent shape and position of phosphenes; (2) that increased stimulation pulse duration made phosphenes brighter; and (3) that there was no detectable interaction between neighboring electrodes which were as close as 2.4 mm apart.
[0006] As intraocular surgical techniques have advanced, it has become possible to apply stimulation on small groups and even on individual retinal cells to generate focused phosphenes through devices implanted within the eye itself. This has sparked renewed interest in developing methods and apparati to aid the visually impaired. Specifically, great effort has been expended in the area of intraocular retinal prosthesis devices in an effort to restore vision in cases where blindness is caused by photoreceptor degenerative retinal diseases such as retinitis pigmentosa and age related macular degeneration which affect millions of people worldwide.
[0007] Neural tissue can be artificially stimulated and activated by prosthetic devices that pass pulses of electrical current through electrodes on such a device. The passage of current causes changes in electrical potentials across visual neuronal membranes, which can initiate visual neuron action potentials, which are the means of information transfer in the nervous system.
[0008] Based on this mechanism, it is possible to input information into the nervous system by coding the information as a sequence of electrical pulses which are relayed to the nervous system via the prosthetic device. In this way, it is possible to provide artificial sensations including vision.
[0009] One typical application of neural tissue stimulation is in the rehabilitation of the blind. Some forms of blindness involve selective loss of the light sensitive transducers of the retina. Other retinal neurons remain viable, however, and may be activated in the manner described above by placement of a prosthetic electrode device on the inner (toward the vitreous) retinal surface (epiretial). This placement must be mechanically stable, minimize the distance between the device electrodes and the visual neurons, and avoid undue compression of the visual neurons.
[0010] Dawson and Radtke stimulated cat's retina by direct electrical stimulation of the retinal ganglion cell layer. These experimenters placed nine and then fourteen electrodes upon the inner retinal layer (i.e., primarily the ganglion cell layer) of two cats. Their experiments suggested that electrical stimulation of the retina with 30 to 100 μA current resulted in visual cortical responses. These experiments were carried out with needle-shaped electrodes that penetrated the surface of the retina (see also U.S. Pat. No. 4,628,933 to Michelson).
[0011] In U.S. Pat. No. 3,699,970 “Striate Cortex Stimulator” to Giles Skey Brindley et al. an implantable device is disclosed comprising a plurality of electrodes for stimulating the striate cortex.
[0012] In U.S. Pat. No. 4,487,652 “Slope. Etch of Polyimide” to Carl W. Amgren a semiconductor having an insulating layer overlying a metal layer is disclosed, wherein the insulator comprises an upper oxide layer, an intermediate polyimide layer, and a lower oxide layer in contact with the metal layer, a method for etching a via from an upper surface of the polyimide layer to the metal layer comprising the steps of applying photoresist; etching an opening from an upper surface of the photoresist layer to the upper oxide layer at a location for forming the via so that an upper surface of the upper oxide layer is exposed at the via location; heating the photoresist to cause a more gradual slope of the photoresist layer from the upper surface of the upper oxide layer at the via location to the upper surface of the photoresist layer; applying reactive ion etchant with a predetermined selectivity between photoresist and oxide to transfer the slope of the photoresist layer to the upper oxide layer at a predetermined ratio; and applying a reactive ion etchant with a predetermined selectivity between oxide and polyimide to transfer the slope of the upper oxide layer to the polyimide layer at a predetermined ratio, whereby the lower oxide layer is simultaneously etched to expose the metal layer at the via location.
[0013] In U.S. Pat. No. 4,573,481 “Implantable Electrode Array” to Leo A. Bullara an electrode assembly for surgical implantation on a nerve of the peripheral nerve system is disclosed.
[0014] In U.S. Pat. No. 4,628,933 “Method and Apparatus for Visual Prosthesis” to Robin P. Michelson a visual prosthesis for implantation in the eye in the optical pathway thereof is disclosed.
[0015] In U.S. Pat. No. 4,837,049 “Method of Making an Electrode Array” to Charles L. Byers et al. a very small electrode array which penetrates nerves for sensing electrical activity therein or to provide electrical stimulation is disclosed.
[0016] In U.S. Pat. No. 4,996,629 “Circuit Board with Self-Supporting Connection Between Sides” to Robert A. Christiansen et al. a copper supporting sheet is disclosed having vias for connecting semiconductor chips to surface mount components. A laminate of polyimide has vias corresponding to the supporting layer vias with copper covering those vias.
[0017] In U.S. Pat. No. 5,108,819 “Thin Film Electrical Component” to James W. Heller a thin film electrical component is disclosed comprising a rigid glass carrier plate, a substrate bonded to the rigid glass carrier plate, the substrate comprising a polyimide establishing a bond with the rigid glass carrier plate that is broken upon immersion of the substrate and the rigid glass carrier plate in one of a hot water bath and a warm temperature physiologic saline bath to release the polymer from attachment to the rigid glass carrier plate, and means for providing an electrical circuit, the providing means being bonded to the substrate and undisrupted during release of the substrate from attachment to the rigid glass carrier plate.
[0018] In U.S. Pat. No. 5,109,844 “Retinal Microstimulation” to Eugene. de Juan Jr. et al. a method for stimulating a retinal ganglion cell in a retina without penetrating the retinal basement membrane at the surface of the retina is disclosed.
[0019] In U.S. Pat. No. 5,178,957 “Noble Metal-Polymer Composites and Flexible Thin-Film Conductors Prepared Therefrom” to Vasant V. Kolpe a composite article is disclosed comprising a polymeric support selected from the group consisting of a polyimide, polyethylene terephthalate, and polyester-ether block copolymer having a noble metal deposited directly onto at least one surface, wherein said deposited metal exhibits a peel force of at least about 0.05 kg per millimeter width after 24 hour boiling saline treatment.
[0020] In U.S. Pat. No. 5,215,088 “Three-Dimensional Electrode Device” to Richard A. Norman et al. a three-dimensional electrode device for placing electrodes in close proximity to cell lying at least about 1000 microns below a tissue surface is disclosed.
[0021] In U.S. Pat. No. 5,935,155 “Visual Prosthesis and Method of Using Same” to Mark S. Humayun et al. a visual prosthesis is disclosed comprising a camera for receiving a visual image and generating a visual signal output, retinal tissue stimulation circuitry adapted to be operatively attached to the user's retina, and wireless communication circuitry for transmitting the visual signal output to the retinal tissue stimulation circuitry within the eye.
[0022] In U.S. Pat. No. 6,071,819 “Flexible Skin Incorporating MEMS Technology” to Yu-Chong Tai a method of manufacturing a flexible microelectronic device is disclosed comprising first etching a lower side of a wafer using a first caustic agent; depositing a first layer of aluminum on an upper side of the wafer; patterning the first layer of aluminum; depositing a first layer of polyimide on the upper side of the wafer, covering the first layer of aluminum; depositing a second layer of aluminum on the upper side of the wafer, covering the first layer of polyimide; depositing a second layer of polyimide on the upper side of the wafer, covering the second layer of aluminum; depositing a third layer of aluminum on the lower side of the wafer; patterning the third layer of aluminum; second etching the lower side of the wafer using the third layer of aluminum as a mask and the first layer of aluminum as an etch stop and using a less caustic agent than said first caustic agent, such that the wafer is divided into islands with gaps surrounding each island; and depositing a third layer of polyimide on the lower side of the wafer, such that the gaps are at least partially filled.
[0023] In U.S. Pat. No. 6,324,429 “Chronically Implantable Retinal Prosthesis” to Doug Shire et al. an apparatus is disclosed which is in contact with the inner surface of the retina and electrically stimulates at least a portion of the surface of the retina.
[0024] In U.S. Pat. No. 6,374,143 “Modiolar Hugging Electrode Array” to Peter G. Berrang et al. a cochlear electrode array for stimulating auditory processes is disclosed.
[0025] In U.S. Pat. No. 6,847,847 “Retina Implant Assembly and Methods for Manufacturing the Same” to Wilfried Nisch et al. a retina implant is disclosed comprising a chip in subretinal contact with the retina and a receiver coil for inductively coupling there into electromagnetic energy.
[0026] In U.S. patent application Ser. No. 20010037061 A1, “Microcontact structure for neuroprostheses for implantation on nerve tissue and method therefore” to Rolf Eckmiller et al. a four layer microcontact structure is disclosed in which the active connection between the microcontact structure and the nerve tissue is brought about by electrical stimulation. The layer adjacent to the nerve tissue to be stimulated is composed of the polymer polyimide and contains penetrating electrodes made of platinum which forms the adjoining layer. There follows a further layer of the polyimide and a layer of the polymer polyurethane. Polyurethane has the property of thermal expansion relative to polyimide.
[0027] In U.S. patent application Ser. No. 2003/0158588 A1 “Minimal Invasive Retinal Prosthesis” to John F. Rizzo et al. a retinal prosthesis is disclosed comprising an RF coil attached to the outside of and moving with an eye to receive power from an external power source; electronic circuitry attached to and moving with the eye and electrically connected to the RF coil; a light sensitive array electrically connected to the electronic circuitry and located within the eye for receiving incident light and for generating an electrical signal in response to the incident light; and a stimulating array abutting a retina of the eye and electrically connected to the electronic circuitry to stimulate retinal tissue in response to the electrical signal from the light sensitive array. A supporting silicone substrate has a polyimide layer spun onto its surface and cured. The copper or chrome/gold conducting layer is then added and patterned using wet chemical etching or a photoresist lift-off process. Next, a second polyimide layer is spun on, and the regions where circuit components are to be added are exposed by selective dry etching or laser ablation of the upper polyimide layer in the desired areas. Finally, the completed components are removed from their supporting substrate.
[0028] Eugene de Juan Jr. et al. at Duke University Eye Center inserted retinal tacks into retinas in an effort to reattach retinas that had detached from the underlying choroid, which is the source of blood supply for the outer retina and thus the photoreceptors. See for example E. de Juan Jr., et al., “Retinal tacks”, Am J Ophthalmol. 1985 Mar. 15; 99 (3):272-4.
[0029] Hansjoerg Beutel et al. at the Fraunhofer Institute for Biomedical Engineering IBMT demonstrated the bonding of a gold ball by force, temperature, and ultrasound onto an aluminum metal layer. See for example Hansjoerg Beutel, Thomas Stieglitz, Joerg-Uwe Meyer: “Versatile Microflex-Based Interconnection Technique,” Proc. SPIE Conf. on Smart Electronics and MEMS, San Diego, Calif., March 1998, vol. 3328, pp 174-182. A robust bond can be achieved in this way. However, encapsulation proves difficult to effectively implement with this method. Gold, while biocompatible, is not completely stable under the conditions present in an implant device since it dissolves by electromigration when implanted in living tissue and subject to an electric current. See for example Marcel Pourbaix: “Atlas of Electrochemical Equilibria in Aqueous Solutions”, National Association of Corrosion Engineers, Houston, 1974, pp 399-405.
[0030] A system for retinal stimulation comprising a polyimide-based electrodes being coated with platinum black are described by Andreas Schneider and Thomas Stieglitz. See for example Andreas Schneider, Thomas Stieglitz: “Implantable Flexible Electrodes for Functional Electrical Stimulation”, Medical Device Technology, 2004.
[0031] It is known that circadian rhythms drive our body's natural cycles of wake and sleep. The hormone melatonin is produced in increasing quantities in the evening and lesser quantities in the morning. Blind people generally do not have normal circadian rhythms and do not produced extra melatonin in the evening. Hence, the perception of light, at least in part, drives the circadian rhythm and the production of melatonin.
SUMMARY OF THE INVENTION
[0032] Present invention is a method of improving circadian rhythms in blind people by stimulation the visual neural system. Ideally a retinal prosthesis of the type used to restore vision can be used to restore normal circadian rhythms. Additionally, brightness on the prosthesis can be increased in the morning and decreased in the evening to stimulate normal circadian rhythms. Alternatively, if a retinal prosthesis is not preferable, the retinal can be stimulated externally, during the day and not at night. While such eternal stimulation can not produced artificial vision, it can stimulate normal circadian rhythms.
[0033] One aspect of the present invention is a visual prosthesis for stimulating circadian rhythms comprising at least one electrode suitable for electrically stimulating visual neurons;
an electrical driver for applying a controlled electrical potential on said electrode; and a timer for controlling activation of said electrical driver.
[0036] Another aspect of the present invention is a flexible circuit electrode array for improving circadian rhythms, comprising
an insulating polymer layer; at least one trace containing a base coating layer, a conducting layer and a top coating layer, embedded in said insulating polymer layer; and at least one electrode connected to said conducting layer of said trace through a via in said insulating polymer layer and said top coating layer.
[0040] Anther aspect of the invention is a method of using a flexible circuit electrode array for manufacturing a visual prosthesis for increasing the melatonin levels at night.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] FIG. 1 depicts a perspective view of the implanted portion of the preferred retinal prosthesis including a twist in the array to reduce the width of a scleratomy and a sleeve to promote sealing of the scleratomy.
[0042] FIG. 2 depicts a perspective view of the implanted portion of the retinal prosthesis showing the fan tail in more detail.
[0043] FIGS. 3 a - 3 e depicts a perspective view of molds for forming the flexible circuit array in a curve.
[0044] FIG. 4 depicts a perspective view of the invention with ribs to help maintain curvature and prevent retinal damage.
[0045] FIG. 5 depicts a top view of a body comprising a flexible circuit electrode array, a flexible circuit cable and a bond pad before it is folded and attached to the implanted portion.
[0046] FIG. 6 depicts a top view of a body comprising a flexible circuit electrode array, a flexible circuit cable and a bond pad after it is folded.
[0047] FIG. 7 depicts a top view of a body comprising a flexible circuit electrode array, a flexible circuit cable and a bond pad after it is folded with a protective skirt.
[0048] FIG. 8 depicts a cross-sectional view of a flexible circuit array with a protective skirt bonded to the back side of the flexible circuit array.
[0049] FIG. 9 depicts a cross-sectional view of a flexible circuit array with a protective skirt bonded to the front side of the flexible circuit array.
[0050] FIG. 10 depicts a cross-sectional view of a flexible circuit array with a protective skirt bonded to the back side of the flexible circuit array and molded around the edges of the flexible circuit array.
[0051] FIG. 11 depicts a cross-sectional view of a flexible circuit array with a protective skirt bonded to the back side of the flexible circuit array and molded around the edges of the flexible circuit array and flush with the front side of the array.
[0052] FIG. 12 depicts a top view of the flexible circuit electrode array.
[0053] FIG. 13 depicts a perspective view of a part of the flexible circuit electrode array.
[0054] FIG. 14 is a graph of experimental data showing patient PB preoperative.
[0055] FIG. 15 is a graph of experimental data showing patient PB postoperative.
[0056] FIG. 16 is a graph of experimental data showing patient TB preoperative.
[0057] FIG. 17 is a graph of experimental data showing patient TB postoperative.
DETAILED DESCRIPTION OF THE INVENTION
[0058] FIG. 1 shows a perspective view of the implanted portion of the preferred retinal prosthesis. A flexible circuit electrode array 10 is mounted by a retinal tack or similar means to the epiretinal surface. The flexible circuit electrode array 10 is electrically coupled by a flexible circuit cable 12 , which pierces the sclera and is electrically coupled to an electronics package 14 , external to the sclera.
[0059] The electronics package 14 is electrically coupled to a secondary inductive coil 16 . Preferably the secondary inductive coil 16 is made from wound wire. Alternatively, the secondary inductive coil 16 may be made from a flexible circuit polymer sandwich with wire traces deposited between layers of flexible circuit polymer. The electronics package 14 and secondary inductive coil 16 are held together by a molded body 18 . The molded body 18 may also include suture tabs 20 . The molded body 18 narrows to form a strap 22 which surrounds the sclera and holds the molded body 18 , secondary inductive coil 16 , and electronics package 14 in place. The molded body 18 , suture tabs 20 and strap 22 are preferably an integrated unit made of silicone elastomer. Silicone elastomer can be formed in a pre-curved shape to match the curvature of a typical sclera. However, silicone remains flexible enough to accommodate implantation and to adapt to variations in the curvature of an individual sclera. The secondary inductive coil 16 and molded body 18 are preferably oval shaped. A strap 22 can better support an oval shaped coil 16 .
[0060] The implanted portion of the retinal prosthesis may include the additional feature of a gentle twist or fold 48 in the flexible circuit cable 12 , where the flexible circuit cable 12 passes through the sclera (scleratomy). The twist 48 may be a simple sharp twist, or fold; or it may be a longer twist, forming a tube. While the tube is rounder, it reduces the flexibility of the flexible circuit cable 12 . A simple fold reduces the width of the flexible circuit cable 12 with only minimal impact on flexibility.
[0061] Further, silicone or other pliable substance may be used to fill the center of the tube or fold 48 formed by the twisted flexible circuit cable 12 . Further it is advantageous to provide a sleeve or coating 50 that promotes healing of the scleratomy. Polymers such as polyimide, which may be used to form the flexible circuit cable 12 and flexible circuit electrode array 10 , are generally very smooth and do not promote a good bond between the flexible circuit cable 12 and scleral tissue. A sleeve or coating 50 of polyester, collagen, silicone, Gore-Tex® or similar material would bond with scleral tissue and promote healing. In particular, a porous material will allow scleral tissue to grow into the pores promoting a good bond.
[0062] The entire implant is attached to and supported by the sclera. An eye moves constantly. The eye moves to scan a scene and also has a jitter motion to improve acuity. Even though such motion is useless in the blind, it often continues long after a person has lost their sight. By placing the device under the rectus muscles with the electronics package 14 in an area of fatty tissue between the rectus muscles, eye motion does not cause any flexing which might fatigue, and eventually damage, the device.
[0063] Human vision provides a field of view that is wider than it is high. This is partially due to fact that we have two eyes, but even a single eye provides a field of view that is approximately 90° high and 140° to 160° degrees wide. It is therefore, advantageous to provide a flexible circuit electrode array 10 that is wider than it is tall. This is equally applicable to a cortical visual array. In which case, the wider dimension is not horizontal on the visual cortex, but corresponds to horizontal in the visual scene.
[0064] FIG. 2 shows a side view of the implanted portion of the retinal prosthesis, in particular, emphasizing the fan tail 24 . When implanting the retinal prosthesis, it is necessary to pass the strap 22 under the eye muscles to surround the sclera. The secondary inductive coil 16 and molded body 18 must also follow the strap 22 under the lateral rectus muscle on the side of the sclera. The implanted portion of the retinal prosthesis is very delicate. It is easy to tear the molded body 18 or break wires in the secondary inductive coil 16 . In order to allow the molded body 18 to slide smoothly under the lateral rectus muscle, the molded body 18 is shaped in the form of a fan tail 24 on the end opposite the electronics package 14 .
[0065] The flexible circuit electrode array 10 is a made by the following process. First, a layer of polymer is applied to a supporting substrate (not part of the array) such as glass. The polymer layer or films of the present invention can be made, for example, any one of the various polyfluorocarbons, polyethylene, polypropylene, polyimide, polyamide, silicone or other biologically inert organic polymers. Layers may be applied by spinning, meniscus coating, casting, sputtering or other physical or chemical vapor deposition, or similar process. Subsequently, a metal layer is applied to the polymer. The metal is patterned by photolithographic process. Preferably, a photoresist is applied and patterned by photolithography followed by a wet etch of the unprotected metal. Alternatively, the metal can be patterned by lift-off technique, laser ablation or direct write techniques.
[0066] It is advantageous to make the metal thicker at the electrode and bond pad to improve electrical continuity. This can be accomplished through any of the above methods or electroplating. Then, the top layer of polymer is applied over the metal. Openings in the top layer for electrical contact to the electronics package 14 and the flexible circuit electrode array 10 may be accomplished by laser ablation or reactive ion etching (RIE) or photolithograph and wet etch. Making the electrode openings in the top layer smaller than the electrodes promotes adhesion by avoiding delaminating around the electrode edges.
[0067] The pressure applied against the retina by the flexible circuit electrode array 10 is critical. Too little pressure causes increased electrical resistance between the array and retina. Common flexible circuit fabrication techniques such as photolithography generally require that a flexible circuit electrode array 10 be made flat. Since the retina is spherical, a flat array will necessarily apply more pressure near its edges, than at its center. With most polymers, it is possible to curve them when heated in a mold. By applying the right amount of heat to a completed array, a curve can be induced that matches the curve of the retina. To minimize warping, it is often advantageous to repeatedly heat the flexible circuit in multiple molds, each with a decreasing radius. FIG. 3 illustrates a series of molds according to the preferred embodiment. Since the flexible circuit will maintain a constant length, the curvature 30 must be slowly increased along that length. As the curvature 30 decreases in successive molds ( FIGS. 3 a - 3 e ) the straight line length between ends 32 and 34 , must decrease to keep the length along the curvature 30 constant, where mold 3 E approximates the curvature 30 of the retina or other desired neural tissue. The molds provide a further opening 36 for the flexible circuit cable 12 of the array to exit the mold without excessive curvature.
[0068] It should be noted that suitable polymers include thermoplastic materials and thermoset materials. While a thermoplastic material will provide some stretch when heated a thermoset material will not. The successive molds are, therefore, advantageous only with a thermoplastic material. A thermoset material works as well in a single mold as it will with successive smaller molds. It should be noted that, particularly with a thermoset material, excessive curvature 30 in three dimensions will cause the polymer material to wrinkle at the edges. This can cause damage to both the array and the retina. Hence, the amount of curvature 30 is a compromise between the desired curvature, array surface area, and the properties of the material.
[0069] Referring to FIG. 4 , the edges of the polymer layers are often sharp. There is a risk that the sharp edges of a flexible circuit will cut into delicate retinal tissue. It is advantageous to add a soft material, such as silicone, to the edges of a flexible circuit electrode array 10 to round the edges and protect the retina. Silicone around the entire edge may make the flexible circuit less flexible. It is advantageous to provide silicone bumpers or ribs to hold the edge of the flexible circuit electrode array 10 away from the retinal tissue. Curvature fits against the retina. The leading edge 44 is most likely to cause damage and is therefore fit with molded silicone bumper. Also, edge 46 , where the array lifts off the retina can cause damage and should be fit with a bumper. Any space along the side edges of curvature may cause damage and may be fit with bumpers as well. It is also possible for the flexible circuit cable 12 of the electrode array to contact the retina. It is, therefore, advantageous to add periodic bumpers along the cable 12 .
[0070] It is also advantageous to create a reverse curve or service loop in the flexible circuit cable 12 of the flexible circuit electrode array 10 to gently lift the flexible circuit cable 12 off the retina and curve it away from the retina, before it pierces the sclera at a scleratomy. It is not necessary to heat curve the service loop as described above, the flexible circuit electrode array 10 can simply be bent or creased upon implantation. This service loop reduces the likelihood of any stress exerted extraocularly from being transmitted to the electrode region and retina. It also provides for accommodation of a range of eye sizes.
[0071] With existing technology, it is necessary to place the implanted control electronics outside of the sclera, while a retinal flexible circuit electrode array 10 must be inside the sclera in order to contact the retina. The sclera must be cut through at the pars plana, forming a scleratomy, and the flexible circuit passed through the scleratomy. A flexible circuit is thin but wide. The more electrode wires, the wider the flexible circuit must be. It is difficult to seal a scleratomy over a flexible circuit wide enough to support enough wires for a high resolution array.
[0072] FIG. 5 shows a body 1 containing the flexible circuit electrode array 10 , the flexible circuit cable 12 and the interconnection pad 52 prior to folding and attaching the array to the electronics package 14 . At one end of the flexible circuit cable 12 is an interconnection pad 52 for connection to the electronics package 14 . At the other end of the flexible circuit cable 12 is the flexible circuit electrode array 10 . Further, an attachment point 54 is provided near the flexible circuit electrode array 10 . A retina tack (not shown) is placed through the attachment point 54 to hold the flexible circuit electrode array 10 to the retina. A stress relief 55 is provided surrounding the attachment point 54 . The stress relief 55 may be made of a softer polymer than the flexible circuit, or it may include cutouts or thinning of the polymer to reduce the stress transmitted from the retina tack to the flexible circuit electrode array 10 . The flexible circuit cable 12 is formed in a dog leg pattern so than when it is folded at fold 48 it effectively forms a straight flexible circuit cable 12 with a narrower portion at the fold 48 for passing through the scleratomy.
[0073] FIG. 6 shows the flexible circuit electrode array 10 after the flexible circuit cable 12 is folded at the fold 48 to form a narrowed section. The flexible circuit cable 12 may include a twist or tube shape as well. With a retinal prosthesis as shown in FIG. 1 , the interconnection pad 52 for connection to the electronics package 14 and the flexible circuit electrode array 10 are on opposite side of the flexible circuit. This requires patterning, in some manner, both the base polymer layer and the top polymer layer. By folding the flexible circuit cable 12 of the flexible circuit electrode array 10 , the openings for the bond pad 52 and the electrodes are on the top polymer layer and only the top polymer layer needs to be patterned.
[0074] Also, since the narrowed portion of the flexible circuit cable 12 pierces the sclera, shoulders formed by opposite ends of the narrowed portion help prevent the flexible circuit cable 12 from moving through the sclera. It may be further advantageous to add ribs or bumps of silicone or similar material to the shoulders to further prevent the flexible circuit cable 12 from moving through the sclera.
[0075] Further it is advantageous to provide a suture tab 56 in the flexible circuit body near the electronics package 14 to prevent any movement in the electronics package 14 from being transmitted to the flexible circuit electrode array 10 . Alternatively, a segment of the flexible circuit cable 12 can be reinforced to permit it to be secured directly with a suture.
[0076] An alternative to the bumpers described in FIG. 4 , is a skirt of silicone or other pliable material as shown in FIGS. 5 to 7 . A skirt 60 covers the flexible circuit electrode array 10 , and extends beyond its edges. It is further advantageous to include windows 62 adjacent to the attachment point 54 to spread any stress of attachment over a larger area of the retina. There are several ways of forming and bonding the skirt 60 . The skirt 60 may be directly bonded through surface activation or indirectly bonded using an adhesive as shown in FIG. 7 .
[0077] Alternatively, a flexible circuit electrode array 10 may be layered using different polymers for each layer. Using too soft of a polymer may allow too much stretch and break the metal traces. Too hard of a polymer may cause damage to delicate neural tissue. Hence a relatively hard polymer, such a polyimide may be used for the bottom layer and a relatively softer polymer such a silicone may be used for the top layer including an integral skirt to protect delicate neural tissue.
[0078] The simplest solution is to bond the skirt 60 to the back side away from the retina of the flexible circuit electrode array 10 as shown in FIG. 8 . While this is the simplest mechanical solution, sharp edges of the flexible circuit electrode array 10 may contact the delicate retina tissue. Bonding the skirt to the front side toward the retina of the flexible circuit electrode array 10 , as shown in FIG. 9 , will protect the retina from sharp edges of the flexible circuit electrode array 10 . However, a window 62 must be cut in the skirt 60 around the electrodes. Further, it is more difficult to reliably bond the skirt 60 to the flexible circuit electrode array 10 with such a small contact area. This method also creates a space between the electrodes and the retina which will reduce efficiency and broaden the electrical field distribution of each electrode. Broadening the electric field distribution will limit the possible resolution of the flexible circuit electrode array 10 .
[0079] FIG. 8 shows another structure where the skirt 60 is bonded to the back side of the flexible circuit electrode array 10 , but curves around any sharp edges of the flexible circuit electrode array 10 to protect the retina. This gives a strong bond and protects the flexible circuit electrode array 10 edges. Because it is bonded to the back side and molded around the edges, rather than bonded to the front side, of the flexible circuit electrode array 10 , the portion extending beyond the front side of the flexible circuit electrode array 10 can be much smaller. This limits any additional spacing between the electrodes and the retinal tissue.
[0080] FIG. 9 , shows a flexible circuit electrode array 10 similar to FIG. 10 , with the skirt 60 , flush with the front side of the flexible circuit electrode array 10 rather than extending beyond the front side. While this is more difficult to manufacture, it does not lift the electrodes off the retinal surface as with the array in FIG. 10 . It should be noted that FIGS. 8, 10 , and 11 show skirt 60 material along the back of the flexible circuit electrode array 10 that is not necessary other than for bonding purposes. If there is sufficient bond with the flexible circuit electrode array 10 , it may be advantageous to thin or remove portions of the skirt 60 material for weight reduction.
[0081] The electrode of the present invention preferably contains platinum. Platinum can be present in any form in the electrode. The electrode has preferably increased surface area for greater ability to transfer charge and also having sufficient physical and structural strength to withstand physical stress encountered in its intended use. The electrode contains platinum having a fractal configuration so called platinum gray with an increase in surface area of at least 5 times when compared to shiny platinum of the same geometry and also having improved resistance to physical stress when compared to platinum black. Platinum gray is described in US 2003/0192784 “Platinum Electrode and Method for Manufacturing the Same” to David Zhou, the disclosure of which is incorporated herein by reference. The electrodes of the preferred embodiment are too small to display a color without significant magnification. The process of electroplating the surface coating of platinum gray comprising plating at a moderate rate, i.e., at a rate that is faster than the rate necessary to produce shiny platinum and that is less than the rate necessary to produce platinum black.
[0082] The flexible circuit electrode array 10 is manufactured in layers. A base layer of polymer is laid down, commonly by some form of chemical vapor deposition, spinning, meniscus coating or casting on a supporting rigid substrate like glass. A layer of metal (preferably platinum), preferably sandwich by layers of another metal for example titanium, is applied to the polymer base layer and patterned to create electrodes and traces for those electrodes. Patterning is commonly done by photolithographic methods. The electrodes may be built up by electroplating or similar method to increase the surface area of the electrode and to allow for some reduction in the electrode over time. Similar plating may also be applied to the bond pads. See FIGS. 5 to 7 . A top polymer layer is applied over the metal layer and patterned to leave openings for the electrodes, or openings are created later by means such as laser ablation. It is advantageous to allow an overlap of the top polymer layer over the electrodes to promote better adhesion between the layers, and to avoid increased electrode reduction along their edges. Alternatively, multiple alternating layers of metal and polymer may be applied to obtain more metal traces within a given width.
[0083] FIG. 12 shows an enlarged top view of the flexible circuit electrode array 10 which is a part of the body 1 as shown for example in FIG. 5 . The preferred positions of the electrodes 78 and the preferred wiring by the trace metal 79 both embedded in the polymer 71 are shown in the FIG. 12 .
[0084] FIG. 13 shows a three dimensional view of a part of the flexible circuit electrode array 10 . It shows one electrode 78 which has a contact with the trace metal 79 . It also shows that the trace metal 79 overlaps the electrode 78 and the electrode 78 overlaps the via in the polymer 71 . The FIG. 13 further shows the adhesion of the polymer 71 with the trace metal 79 and the electrode 78 which results in a very high effective insulation of the trace metal 79 and the electrode 78 . FIG. 13 shows also that the trace metal 79 is preferably composed of platinum conducting trace 73 covered on the lower and upper side preferably with a thin titanium layer 72 a and 72 b . FIG. 13 finally shows that the first applied base polymer 71 a and the subsequently applied top polymer layer 71 b form a single polymer layer 71 .
[0085] FIG. 14 shows melatonin levels for a first patient, PB, preoperative. The vertical axis is melatonin levels as measured with a mouth swab every four hours. The horizontal axis is time, where the shaded portions are normal night time hours, over a four day period. There is no significant increase in melatonin levels at night. In fact melatonin decreased on average during the night time periods.
[0086] FIG. 15 shows the same patient, as in FIG. 14 , using the retinal prosthesis of the current invention. Melatonin levels increased, on average, during the night time hours.
[0087] FIG. 16 shows a second patient TB, preoperative with, on average increased melatonin levels at night, but inconsistent results.
[0088] FIG. 17 shows the second patent, as in FIG. 16 , using the retinal prosthesis of the current invention. Melatonin level increase significantly, and consistently.
[0089] An alternative embodiment of the present invention can be used when surgery is not desired due to health or surgical apprehension. An external electrode can be attached to the cornea in a form similar to a contact lens, or mounted to the inside of a pair of dark glasses. While such external electrodes can not created formed vision, they can create artificial light during the daytime and be turned, or removed, to create artificial darkness at night. Such an electrode would make it possible to control and improve the melatonin production for patients who are not necessarily vision impaired or blind.
[0090] The present invention will be further illustrated by the following examples, but it is to be understood that the invention is not meant to be limited to the details described herein.
EXAMPLES
[0091] In the present example the inventors modulate the above system artificially through retinal prostheses in two patients with retinitis pigmentosa.
[0092] Two patients TB and PB who had retinitis pigmentosa and no light perception (NLP) for five (5) and twenty (20) years were examined. The two patients and a normal control had a multiple saliva samples taken over the course of four (4) days and assayed for melatonin. The two patients then had surgical implantation of the retinal prosthetic implant. The prosthesis was electrically stimulated in one subject. The patients and the normal control were then evaluated with several saliva sampling over the course of four (4) days.
[0093] Melatonin concentrations in saliva samples were measured using a commercially availably melatonin ELISA assay (n=83) from ALPCO Diagnostic, Windham, N.H. 03087. Concentrations were calculated by fitting to a standard logistic equation. A cosinor analysis was performed on the data set using commercially available software from Expert Soft Tech.
[0094] The normal control showed typical circadian levels of melatonin with morning peaks and day time lows with a period of 1430 minutes (24 hours=1440 minutes) an about 62% rhythm.
[0095] Both patients with advanced retinitis pigmentosa showed decreased periodicity of melatonin levels preoperatively. Patient PB exhibited a period of 925 minutes with 21% rhythm. While the period could not be calculated for patient TB, he displayed 39% rhythm.
[0096] Patient PB did not show preoperative significant increase in melatonin levels at night. In fact melatonin decreased on average during the night time periods as shown in the shaded normal night time hours over four day period in FIG. 14 .
[0097] Patient TB showed preoperative on average increased melatonin levels at night, but inconsistent results as shown in the shaded normal night time hours over four day period in FIG. 16 .
[0098] After surgical implantation of the retinal prosthetic, both patients PB and TB with or without prosthetic stimulation showed doubling of the percent rhythm and a normalization of their periods 1360 and 1430 minutes as would be expected from a normal circadian rhythm.
[0099] Patient PB after using the retinal prosthesis of the current invention showed significant increase in melatonin levels at night as shown in the shaded normal night time hours over four day period in FIG. 15 .
[0100] Patient TB showed after using the retinal prosthesis of the current invention a significant consistent increase in melatonin levels at night as shown in the shaded normal night time hours over four day period in FIG. 17 .
[0101] The data suggest that entrainment of circadian rhythms is possible in patients with retinitis pigmentosa, and that the retinohypothalamic pathway that modulates circadian rhythms is intact.
[0102] The data additionally suggest that it is possible to recover entrainment of the circadian rhythm with implantation surgery.
[0103] Accordingly, an improved method making a visual prosthesis and improved method of stimulating neural tissue has been shown. While the invention has been described by means of specific embodiments and applications thereof, it is understood that numerous modifications and variations could be made thereto by those skilled in the art without departing from the spirit and scope of the invention. It is therefore to be understood that within the scope of the claims, the invention may be practiced otherwise than as specifically described herein.
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Present invention is a method of improving circadian rhythms in blind people by stimulation the visual neural system. Ideally a retinal prosthesis of the type used to restore vision can be used to restore normal circadian rhythms. Additionally, brightness on the prosthesis can be increased in the morning and decreased in the evening to stimulate normal Circadian rhythms. Alternatively, if a retinal prosthesis is not preferable, the retina can be stimulated externally, during the day and not at night. While such eternal stimulation can not produced artificial vision, it can stimulate normal circadian rhythms.
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This application is a continuation-in-part of my application Ser. No. 143,016, filed Jan. 12, 1988. Said prior patent application Ser. No. 143,016, now abandoned, was in turn a continuation-in-part of my U.S. patent application Ser. No. 887,811, filed in the U.S. Patent and Trademark Office on July 21, 1986, and entitled "Improved Backhoe", now U.S. Pat. No. 4,720,234 issued Jan. 19, 1988.
BACKGROUND OF THE INVENTION
This invention was conceived as a solution to the problem of providing a swing tower mechanism and backhoe assembly which possesses two advantages not found together in prior art machines. One advantage is improved balance, i.e., retraction closer to the tractor rear when the backhoe is being transported. The other is ready detachability of the backhoe.
As shown in my copending U.S. Pat. No. 4,720,234 , various backhoe arrangements have been devised in efforts to improve operator visibility and bring the center of gravity of the backhoe closer to the tractor when the backhoe is being transported. These are:
First, that of U.S. Pat. No. 3,376,984 to Long and Shumaker, featuring a boom and two outboard boom cylinders, all pivotally mounted on a swing tower so that the boom cylinders flank the boom in a clearance relationship;
Second, that of U.S. Pat. No. 3,987,914 to VanDerZyl, McMullen and Kraske, in which the boom is constructed in two sections, with the boom cylinder having its cylinder side pivotally secured directly to the swing tower;
Third, that of U.S. Pat. No. 4,074,821 to Long, featuring a boom cylinder and two outboard boom sections which flank the cylinder; and
Fourth, that of U.S. Pat. No. 4,358,240 to Shumaker, in which the boom and boom cylinder are pivotally mounted in offset relation on a swing tower.
Each prior art structure suffers from one or more of the following limitations: Obstruction of the operator's view, lack of practical detachability, or insufficient achievement of good balance during transport of the backhoe. In providing a solution which is relatively free of the disadvantages and limitations of the prior art, I conceived of a swing tower mechanism in which the backhoe assembly proper is mounted on a rocker, which shifts the backhoe assembly between transport and working positions, making a substantial improvement in the balance of the tractor-backhoe ensemble. In the improved backhoe of my U.S. Pat. No. 4,720,234, I positioned the bucket on the ground and used thrust of the boom cylinder against the rocker to put the rocker in transport mode and enable the backhoe to go into transport position. I later conceived the idea that the rocker positioning could be controlled from the swing tower by mounting a rocker-control hydraulic cylinder on the swing tower. Then positioning of the rocker could be controlled without depending on the subordinate machine. This led to the perception that the combination of swing tower, rocker and rocker-actuating cylinder constituted the basis for a three-point hitch, so that now a tractor suitable for a backhoe could be used to support, transport, elevate and depress, lift, tow, move in azimuth or allow to move in azimuth, a wide range of subordinate machines; for example, the blade 52 of FIGS. 13 and 14. Optionally, a hydraulic motor with power-takeoff shaft can also be mounted on the rocker (FIGS. 11, 16, 17). Such a power takeoff, being carried by the rocker, automatically moves in elevation and azimuth with the subordinate vehicle or machine. Thus, the combination of swing tower, rocker, and hydraulic actuator, with the capacity to transport and position the rocker load, has very wide application.
SUMMARY OF THE INVENTION
The major respects in which the instant disclosure departs from that of the originally filed patent application are: The addition of the actuator mounted on the swing tower and the provision of various types of rockers, both changes greatly expanding the field of utility of the invention. Further, a power takeoff is mounted on the rocker.
The preferred embodiment of the invention is first shown as coupling a backhoe assembly to a tractor. In that environment the invention is in the category of structures intended to bring the dipper assembly in closer to the tractor during transport. The invention has further utility in towing and elevational positioning of various subordinate loads or machines. It is of particular advantage when providing a three-point hitch.
OBJECTS
The primary object of the invention is to provide swing tower, rocker and 3-point hitch combinations for coupling a subordinate machine to a tractor in such a way as to accomplish controlled and positive positioning of the subordinate machine in azimuth and throughout a range of elevation including transport and working positions.
Another object of the invention is to provide a swing tower arrangement featuring a rocker and actuating means mounted on the swing tower for positioning the rocker in elevation, the rocker being formed to govern the positioning and transport of the subordinate mechanism.
It is also an object of the invention to provide a power takeoff mechanism carried by the rocker and therefore movable in elevation and azimuth with the subordinate machine.
An object of the invention is further to provide a swing tower mounting frame and three-point hitch arrangement capable of controlling the transport and positioning in elevation and azimuth of a drawn and/or supported load.
Yet another object of the invention is to improve the swing tower arrangement disclosed in my aforesaid U.S. Pat. No. 4,720,234, in such a way as to provide elevational control by means on the swing tower, thereby to extend the range and types of load that can be towed by the tractor vehicle.
A general object of the invention is to realize the full capabilities of the combination of hitch frame or rocker, swing tower and azimuth and elevational actuators as a hitching structure with a wide range of subordinate machines or loads.
DRAWINGS
For a better understanding of the invention, together with other objects, advantages and capabilites thereof, reference is made to the following description of the accompanying drawings, in which:
FIG. 1 is a side elevational view of a preferred form of my novel swing-tower mechanism as incorporated in a backhoe, showing the backhoe assembly proper in its retracted or transport position (rocker counter-clockwise);
FIG. 2 is a side elevational view of my novel swing-tower mechanism, as incorporated in the FIG. 1 backhoe, showing the relationships of the swing tower, means adapted to be secured to a tractor for mounting it, means for positioning the tower in azimuth, the rocker, and means for positioning the rocker in elevation;
FIG. 3 is a side elevational view of my novel swing tower mechanism, generally resembling FIGS. 1 and 2, except for the substitution of an alternate form of rocker adapted to provide a three-point hitch arrangement, for towing and positioning in elevation a subordinate machine, the parts being shown in working position, wherein the upper hydraulic cylinder rod is extended to hold the rocker in clockwise position, corresponding to the lowered or working position of whatever subordinate machine is hitched to the rocker;
FIG. 4 is a top view of the FIG. 2 or FIG. 3 mechanism with the rocker removed;
FIGS. 5 and 6 are sectional views of the FIG. 2 or FIG. 3 mechanism, as taken along the respective section lines 5--5 and 6--6 of FIG. 3;
FIG. 7 is an end elevational view of the FIG. 2 or FIG. 3 mechanism, as taken from the line of view indicated by the arrows 7--7;
FIG. 8 is a perspective view of the pivot shaft and split ring which provide support for the rocker of the FIG. 2 or FIG. 3 mechanism;
FIG. 9 shows the backhoe assembly of FIG. 1, as removed from the swing tower, the rocker being shown in clockwise or working position and the boom and boom cylinder being shown in working position;
FIGS. 10, 11, and 12 are, respectively, front elevation, right end and rear views of the rocker of the FIG. 2 mechanism, FIG. 11 being broken to show details of the journal for the pivot shaft on which the rocker is mounted;
FIGS. 13 and 14 are side elevational and top views of the invention, as incorporated in a three-point hitch coupling for a tractor and a subordinate mechanism, such as a blade, an alternate form of rocker as shown in FIG. 3 and 15 being used;
FIG. 15 is a right end view of the rocker of FIG. 3, 13, 14, as taken from the line of view indicated by arrows 15--15. This figure also shows the power takeoff 119-120 of FIGS. 16, 17.
FIGS. 16 and 17 are side elevational and top views corresponding to FIGS. 13 and 14, respectively, but with the addition of a power takeoff shaft and hydraulic motor for same, said motor being mounted on the rocker for movement therewith, FIG. 16 also showing an optional drawbar 126.
FIGS. 18 and 19 are side elevational and fragmentary views of the specific embodiment of swing tower, three-point hitch and azimuth and elevational positioning arrangement in which the hitch frame is secured to the swing tower and the elevational actuating means is mounted on the hitch frame. FIG. 19 is exploded to show the relationships among hitch-adjusting parts.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown a novel position control and transport mechanism, as used in coupling tractor 20 (or other tractive vehicle) to a subordinate machine (in this figure a backhoe assembly). Secured to tractor 20 are vertically spaced upper and lower plates 21 and 22, constituting with pivot shafts 50 and 51 means for mounting a swing tower for movement in azimuth. A swing tower 23, formed with top and bottom plates 24 and 25 and side plates 26 and 27 (FIGS. 1 and 4) is accordingly mounted by pivot shafts 50 and 51 on the brackets 21, 22. In accordance with the invention, a rocker 28 is swingably mounted for movement in elevation on the swing tower by a generally horizontally extending shaft 30 projecting through side walls 26, 27 (FIG. 1, 4, and 5). Integral bosses 65, 66 (FIGS. 4, 5) are formed in side walls 26, 27, respectively, in order to provide journals for shaft 30. The expression "in elevation" as used herein is intended to cover angular displacement about a generally horizontal axis, such as shaft 30, whether the displacement is above or below the horizontal. "Elevation" will be understood therefore to include both elevation proper and depression.
In further accord with the invention, there is provided an actuating means or hydraulic cylinder 31, having its rod end pivotally secured to an integral arm 29 on rocker 28 whereby the elevational position and movement of rocker 28 and its subordinate machine (for example, the backhoe assembly of FIG. 9) are determined and controlled. The swing tower is moved and positioned in azimuth by suitable actuators such as the swing cylinders 48 and 49 (FIGS. 1, 4, 5, 6) here shown.
The novel position control and transport mechanism just described has the competence to support, transport, and control both in azimuth and elevation a range of loads and subordinate machines. Note that the rocker 28 articulates at the ends of its arms with the subordinate backhoe in that it is formed with spaced bore pairs 75,76 and 72,72 (accepting shafts 33 and 39, FIG. 11) A bore, 73,74 therebetween (accepting shaft 30) provides a pivot point between the ends of the rocker 28, so that it rocks on shaft 30.
In the FIG. 1 application the subordinate machine is a backhoe assembly. It is shown and described in detail in my U.S. Pat. No. 4,720,234. This mechanism will now be briefly described. A boom 32 is pivotally mounted on the rocker 28 by shaft 33. To the upper end of the boom 32 is pivotally secured, as by shaft 34, a dipper arm 35. The boom is provided with suitably offset and spaced ears 36 and 37. Boom cylinder 38 is pivotally secured to the upper end of the rocker by shaft 39. The rod of this boom cylinder 38 is pivotally secured to ear 36 on boom 32 by shaft 53. Dipper cylinder 40 is pivotally secured at its housing end to ear 37 on the boom 32 by shaft 54. The rod of dipper cylinder 40 is secured to dipper 35 by shaft 41. A bucket cylinder 42 is pivotally secured at its housing end to dipper arm 35 by shaft 43. The rod of bucket cylinder 42 actuates and positions knee joint shaft 47. Links 45 and 46 cooperate with the dipper cylinder rod to control the movement and positioning of bucket 44 which is pivotally mounted by shaft 55 at the working end of the dipper.
Reference is now made to FIG. 2 and 3 for further details pertaining to my novel position and control mechanism. The attribute of subordinate-machine-detachability is achieved in this machine by the arrangement of rocker and shaft 30. This shaft or pin means is formed with an annular groove, such as 56, at each end, and it is fitted with split rings, such as 57 (FIG. 8) so that it can easily be removed. Similar provisions are made for the ready removability of shaft 58 from arm 29 (FIG. 2) and the rod end of rocker cylinder 31. These provisions render very easy the removal of rocker 28 and the substitution of alternate types of rockers, such as the one providing for a three-point hitch as hereinafter described.
The backhoe assembly is easily detached by the removal of shafts 33 and 39 from their respective bores in rocker 28, they being provided with annular grooves and removable split rings for that purpose. Thus the substitution of other types of subordinate machines or loads is facilitated.
Swing cylinders 48 and 49 move the swing tower in azimuth. They are trunnioned for swinging movement between removable upper plate 115 and lower plate 114, the latter plate being on bracket 22 (FIGS. 2-6). They include connecting rods 59 and 60, respectively, pivotally secured to wrist pins 61, 62. The wrist pins are journaled in bores formed in upper bearing plate 63 and lower bearing plate 64 (FIG. 2, 3, 6). The plates 63 and 64 are welded to the sidewalls 26 and 27 of the rocker and they are suitably bored to provide for the wrist pins 61 and 62, and both plates are appropriately formed to permit the turning movement of the semi-circular ends of the rods 59 and 60 which bear the wrist pins, after the manner of connecting rods.
Rocker 28 (FIGS. 10-12) is formed with aligned hubs 68 and 69, a bifurcated upper section 67 and a shorter bifurcated control arm 29 and lower sections comprising relatively widely spaced sides 70 and 71. It will be understood that the left hand element 67 and element 70 of FIG. 11 are in one piece. Similarly, the right hand elements 29 and elements 71 of the same figure are one piece. Bores 72, 72 are formed near the upper ends of the rocker to accept shaft 39. Aligned bores 73 and 74 are provided in the hubs 68 and 69 to accept shaft 30. Bores 75 and 76 are formed near the lower end of the rocker to accept shaft 33. The hubs 68,69 are welded to a tubing 77 to which the other elements of the rocker are welded. Bores 78 in control arm 29 and bore 124 in rod 123 accept shaft 58 (FIGS. 2, 3, 4, 11).
The fittings are as follows: Rocker 28, pivoted on shaft 30, within sidewalls 26, 27; lower end of boom 32, pivoted by shaft 33 and within sides 70, 71 of the rocker; lower end of the boom cylinder 38, pivoted by shaft 39 and within bifurcation 67; end of rod of cylinder 31 bored to accept shaft 58 pivoted in bore 78 (FIG. 11).
DESCRIPTION OF THE THREE-POINT HITCH EMBODIMENT
Before dealing with additional structural details of the mechanism common to FIGS. 1-3, the description proceeds to the invention as supplying a three-point hitch between a tractor and a type of subordinate mechanism other than a backhoe. Referring now to FIGS. 3, 13, 14, and 15, there is shown a different version of rocker, generally designated as 79, and associated elements together constituting a three-point hitch. The main body of rocker 79 is roughly of quadrangular configuration with concavities on the face and top and a truncated lower rear (as best shown in FIG. 3), generally centrally of which rear are provided the bores for accepting shaft 30. The rocker 79 is fitted on the shaft and is controlled by the rocker cylinder 31, acting through shaft 58 in the same manner as with rocker 28. The rocker 79 is used to control the elevational position of the subordinate machine (such as blade 52 or any machine having a three-point hitch attachment).
The three-point attachment on blade 52 (FIG. 12) comprises pivot pins 80, 81, and 82 so located as to form apex points of an imaginary triangle. Each of these pivot pins is adapted to be secured as by a cotter pin to the ball joints of hitch links. A three-point hitch is formed by rocker 79 and the turnbuckle link 84 and links 85, 86 articulated thereto. At their inner ends the elements 84, 85 and 86 are secured by suitable ball joints to the pin portions 89, 90 and 91 respectively. Pin formations 90 and 91 are on the ends of lower rocker bar 94 (FIG. 15), and pin 89 is secured to a triangular bifurcation 93, welded to bar 95 (best shown in FIG. 13). Bifurcation 93 is provided with several generally vertically aligned bores, such as 92 (FIG. 15) to provide for adjustable positioning of the pivot pin 89. Bar 95 has pin ends 130 and 131. The rocker 79 (FIG. 15) is formed by plates 96 and 97. Bar 95 corresponds in position to shaft 39 (FIG. 1) and is secured to plates 96, 97. Adjustable straps 133 and 134 (FIGS. 13-14) are pivoted on bar 94 near its midpoint and their outer ends are pivoted to links 85, 86 near their midpoints. Bar 94 corresponds in position to shaft 33 and likewise projects through the plates 96, 97. Tube 98 connects the plates. Press fitted to the tube are hubs 99, 100, providing bores 101, 102 for shaft 30. Bifurcated control arm 103 is bored at 104 near its outer end to accept shaft 58, moved by rod 123 of cylinder 31. Adjustable straps 87 and 88 are pivoted to lower bar pins 130 and 131 and pivotally connected at their outer ends to links 85 and 86 to provide height adjustment. The hubs 99 and 100 mount rocker 79 in the same manner as rocker 28. Again, the elements of rocker 79 (FIG. 15) are welded together. From FIGS. 3 and 15 it will be seen that this rocker 79 is a mounting frame for a three-point hitch. This mounting frame has a pivot point 101, 102 in its midsection; i.e., between its end bars 95 and 94, the bars being articulated, respectively to the upper link and the lower link pair of the hitch.
The subordinate machine 52 is towed from the three-point hitch supplied by the rocker assembly 79. Actuator 31 positions the rocker in lift and working positions.
Because shaft 58 follows an arcuate path as rocker 79 shifts, the rocker cylinder is mounted for swinging movement between plate 105 (FIG. 4), welded to plate 24, and plate 106, bolted to plate 24. Trunnion members 107 and 108 are journaled between carriage plates 105 and 106, to secure the rocker cylinder for its small swinging movement so that the shaft 58 can follow the arm 29. The rocker cylinder is generally horizontally disposed to move upper bar 95 closer to the tractor when the rocker is in lifting position and to move bar 94 closer to the tractor when the rocker is depressed to working position.
Provision is made for the removal of the swing tower from the brackets 21, 22. As shown in FIGS. 2, 3, and 7, a lower bifurcated type of connection is provided by bent plate 109 underlying bracket 22. Pivot shaft 51 has an enlarged head and stem projecting through the elements 109, 22, and 25 (FIG. 3). The first step in the separation process is to withdraw pin 51. Another step in the separation process is to remove the wrist pin bearings 61 and 62, they likewise being formed with heads facilitating removal.
Pivot shaft 50 has an offset head 110 (FIG. 3) and a stem projecting through top plate 24, bracket 21, collar 111, and the top of an inverted L-shaped structural member 112, welded between the plates 26, 27 of the swing tower. As best shown in FIGS. 3, 4, 5 and 7, the L-shaped structural member 112 enhances structural rigidity. This member comprises a horizontal shelf portion, a vertical portion, and two gussets (FIGS. 3, 7) supporting the horizontal portion, all welded together. The head 110 of the pivot shaft 50 is rectangular in form and non-symmetrically located (FIGS. 3 and 4).
The swing tower can be locked against movement in azimuth, when desired, by a suitable detent 116, sliding in bores in bracket 21 and the swing tower top plate 24 and positioned by a slotted tilt member 117. This member 117 is spring biased into locking position, but can be tilted by a manually operated rod 118 (FIG. 2) to withdraw the detent.
Referring now to FIGS. 16, 17, which correspond closely to FIGS. 13, 14, respectively, there is shown an optional feature in the form of a power takeoff. A hydraulic motor 119, having a power takeoff shaft 120 is secured by bolts 121, 122 and the like to a U-shaped base 125, welded to the rocker 79. This base is seen in FIG. 15. In the event that a drawbar is desired for simple towing operations, it can be pivoted on the lower rocker bar as shown in FIGS. 16 and 17. The drawbar is designated by reference numeral 126. The drawbar is maintained in relation to the rocker by a U-shaped swinging frame comprising links 127 and 128 interconnected by a cross-member 129 which underlies the drawbar and is pivot-pinned to the rocker. The crossbar is bolted to the rocker as shown.
OPERATION
As to the embodiment of FIG. 1, involving a backhoe, the rocker 28 is positioned counter clockwise to provide for transport of the backhoe assembly. The rocker 28 is depressed to the clockwise position (FIG. 9) as the backhoe is working the ground or otherwise in operation. The shifting of the rocker is accomplished by the rocker cylinder 31. This cylinder, like all the others here involved, is of the double action type. The cylinder 31 greatly enlarges the utility of my novel arrangement because it is not dependent on subordinate machine contours. Once the shifting of the rocker 28 is achieved, the operation will be understood by reference to my U.S. Pat. No. 4,720,234.
As to the three-point hitch embodiment, those versed in the relevant art will perceive that the rocker 79 and associated links constitute such a hitch, working to provide support, tow and lift for the subordinate machines. If the subordinate machine requires a power takeoff, then the structure of FIGS. 16 and 17 not only provides such, but also moves it in elevation and azimuth along with the subordinate machine.
ADDITIONAL EMBODIMENT
In the embodiment of FIGS. 18-19, the 3-point hitch is selectively adjusted to transport and working positions by actuating means independent of the subordinate machine and separate and apart from the tower. The said hitch is secured to the swing tower and the relative angular movement of subordinate machine and swing tower in elevation is achieved by adjustment of the hitch internally. The swing tower has the usual upper and lower plates 136, 25, pivoted on tractor plates 21, 22, respectively. Actuators 48, 59 and 49, 60 (compare FIG. 6) positively and affirmatively swing the tower in azimuth. The 3-point hitch is formed with a frame having side walls such as 141, crossed by lower bar 94 and upper crank shaft 146. An upper link 84 extends from crank shaft short arm 137 to the subordinate machine and a pair of lower links 85, 86 extend from bar 94 to the machine to complete the hitch. Arms 147, 148 are outboard of the journals in the frame walls through which shaft 146 projects. To provide for selective adjustment of the hitch between transport and working positions actuating means 136, preferably hydraulic, is swiveled at its lower end at the middle of cross bar 94 and connected along axis a . . . a at its upper end to short crank 137 on shaft 146. Pivot pin 151 also secures link 84 to crank 137, which lifts and lowers the upper end of link 84. The spaced long arms or cranks 147 and 148 are pivotally linked at their outer ends to lifters 149,150 for lower links 85, 86, respectively, so that the lower links are angularly moved by the bell-crank expedients 147,149 and 148,150. Connections of link 149 and link 150 to arms 147,148 are made by pivot pins, such as 152, along axis b . . . b. The lifters are pivotally connected at lower ends to links 85,86. The frame walls, such as 141, are bored for shaft 146.
The hitch frame may be reinforced by additional cross-bars, not shown, if desired. The frame is mounted on or directly secured to the swing tower by quick-removable means such as a bolt-washer-nut set 139 or a pin and split ring (compare FIG. 8). Elements 21,22,25,26,48,50,51,59,84 through 86,94 and 112 correspond to like-numbered elements of FIGS. 16-17. The hitch frame sides nest within the swing tower sides. The frame is provided with a back wall, facing plate 112. Aligned openings 145 are formed in the side walls of hitch frame and swing tower to permit the use of additional securing means 139, if desired.
While there have been shown and described several embodiments of the invention, it will be understood that various changes and modifications may be made therein without departing from the proper scope of the appended claims.
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This is a swing-tower arrangement for coupling a back-hoe assembly to a tractor or the like. It features a rocker swingable in elevation on the swing tower. An actuator on the swing tower controls the position of the rocker, improving transport and control of the backhoe and making practical the adaptation of the arrangement to a wide range of tows. Detachable rockers are variously used to shift the backhoe assembly to transport and working positions and to tow and lift other types of subordinate machines. A power takeoff is mounted on the rocker.
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DETAILED DESCRIPTION OF THE INVENTION
This invention relates to N-substituted trialkoxybenzyl piperazine derivatives expressed by the following general formula (I): ##STR5## where R and Z represent the same as defined in the claim.
The compounds of this invention are novel materials which are not available in the literature and which have the excellent pharmacodynamic effects on the coronary circulation system such as coronary artery vasodilative action or cardiac movement controlling action and prove useful for medicinal preparations.
The cardiovascular activity of the compounds of this invention, as measured according to Langedorff's method by using the removed guinea pig heart, and LD 50 on mice are shown in Table 1 below. For administration of the compounds of this invention into the human body, it is recommended to give them at the dose of 10 to 500 mg/day for internal administration and 1 to 50 mg/day for intravenous aministration. The compounds can be administered as such or in combination with a pharmaceutical carrier conventionally employed in cardiovascular and like preparations.
Table 1__________________________________________________________________________Cardiovascular activity and LD.sub.50 of thecompounds of this invention CoronaryCon- perfu- Heart Move-Ex- centra- sion ments Heartampletion pressure Ampli- rate LD.sub.59 (mouse)No. (g/ml) (Δ%) tude Tonus (Δ%) mg/kg i.p.__________________________________________________________________________1 10.sup.-4 5.7 ↓ → -18.22 10.sup.-4 -11.1 ↓ → -60.33 10.sup.-4 4.4 ↓ → -21.94 10.sup.-4 -2.1 ↑ → -8.6 5675 10.sup.-4 3.8 → → -9.36 10.sup.-4 -3.7 ↓ → -11.77 10.sup.-4 -18.8 ↓ → -37.5 2398 10.sup.-4 -19.2 ↓ → -19.1 849 10.sup.-4 -10.0 ↓ ↓ -28.610 10.sup.-4 -4.4 ↓ ↓ -10.7 56711 10.sup.-4 -11.1 ↓ → -49.4 33612 10.sup.-4 - 6.5 ↓ → -16.1 72413 10.sup.-4 -16.0 ↓ → -54.5 10614 10.sup.-4 -20.0 ↓ ↓ -48.7 142__________________________________________________________________________
The compounds which are embraced within the scope of this invention can be synthesized by various methods, but the most general and simplest way is to react an alkyl halide or epoxy compound with a trialkoxybenzyl piperazine expressed by the following chemical structural formula (II) or (III): ##STR6## To synthesize a bis-compound, one mole of dihalogenoalkane is reacted with two moles of the material expressed by the above-shown structural formula (II) or (III).
The synthesis of the compounds of this invention may be also accomplished by the trialkoxybenzylation of alkylpiperazines or dipiperazinoalkanes or by the piperazine ring closure using an ethanolamine.
The present invention is described in further detail by way of some embodiments thereof, but it is to be understood that the scope of this invention is not limited to the compounds shown in these embodiments.
EXAMPLE 1 (R: methyl group (same in Examples 2 through 16); Z; Isopropenyl group)
5.0 gr of a hydrochloride of the material (II), 3.3 gr of isopropenyl bromide and 8.1 gr of potassium carbonate anhydride are dissolved in 150 ml of DMF and agitated at 50° C for 1 hour, and after cooling, the reaction product is refined by a silica gel column chromatograph and recrystallized from isopropanol as a hyrochloride. Melting point of the product: 205° - 210 ° C; yield: 2.5 gr. (C 19 H 30 N 2 O 3 .2HCl)
EXAMPLE 2 (Z: cinnamyl group)
5.0 gr of a hydrochloride of the material (II), 3.38 gr of cinnamyl chloride and 8.1 gr of potassium carbonate anhydride are mixed and agitated at 60° C for one hour, and after cooling, the reaction mixture is subjected to the same refining treatment as in Example 1 and then recrystallized from ethanol as a hydrochloride. Melting point (decomposed): 208° C; yield; 4.2 gr. (C 23 H 30 N 2 O 3 .2HCl)
EXAMPLE 3 (Z: diaminotriazine group)
5.0 gr of a hydrochloride of the material (II) is dissolved in 100 ml of ethanol in which 1.2 gr of metallic sodium has been dissolved, and this solution is further added with 4.0 gr of 2,4-diamino-6-chloro-S-triazine and 50 ml of dioxane and refluxed under agitation for 6 hours. The reaction product is evaporated to dryness under vacuum and the residual material is added with dilute caustic soda solution, and the precipitated crystals are filtered out and recrystallized from isopropanol, followed by additional recrystallization from dioxane as a hydrochloride. Melting point: 246° - 250° C; yield:3.06 gr. (C 17 H 25 N 7 O 3 .2HCl)
EXAMPLE 4 (Z: morpholinoethyl group)
10.4 gr of a hydrochloride of the material (II), 6.56 gr of morpholinoethyl chloride and 25.1 gr of potassium carbonate anhydride are dissolved in 150 ml of ethanol and refluxed under agitation for 4 hours, and after cooling, the mixture is subjected to a normal refining treatment and recrystallized from ethanol as a hydrochloride. Melting point (decomposed): 230° C; yield: 3.18 gr. (C 20 H 33 N 3 O 4 .3HCl1/2H 2 O)
EXAMPLE 5 (Z: hydantoinbutyl group)
6.8 gr of a hydrochloride of the material (II), 4.7 gr of bromobutylhydantoin and 5.0 gr of potassium carbonate anhydride are dissolved in 70 ml of DMF and agitated at 50° to 60° C for 2 hours, and the reaction mixture is subjected to a normal refining treatment and recrystallized from hydrous methanol as a hydrochloride. Melting point: 208° - 213° C: (C 21 H 32 N 4 O 5 .2 HCl.H 2 O) yield: 4.0 gr.
EXAMPLE 6 ##STR7##
(same in Example 7 through 9). n = 2)
10.0 gr of a hydrochloride of the material (II), 13 gr of potassium carbonate anhydride and 5.6 gr of dibromoethane are dissolved in 100 ml of DMF and agitated under heating at 50° to 60° C for 3 hours. This mixture is then subjected to a proper treatment according to a normal method and the obtained basic material is recrystallized from acetone. Melting point: 121 - 122° C; yield: 3.9 gr. (C 30 H 46 N 4 O 6 )
EXAMPLE 7 (n = 4)
5.0 gr of a hydrochloride of the material (II), 9.0 gr of potassium carbonate anhydride and 1.0 gr of dichlorobutane are dissolved in 100 ml of DMSO and agitated under heating at 60° to 70° C for 10 hours, and the mixture is treated according to a normal method and the obtained basic material is extracted with chloroform. The chloroform extract is shaked with dilute hydrochloric acid and the hydrochloric acid layer is rendered alkaline, and the object material is extracted with ether. The extract is further added with 4 moles of maleic acid and recrystallized from isopropanol as a maleate. Melting point: 95° - 98° C; (C 32 H 50 N 4 O 6 .4C 4 H 4 O 4 ) yield: 1.50 gr.
EXAMPLE 8 (n = 6)
6.7 gr of a hydrochloride of the material (II), 1.8 gr of dichlorohexane and 7.0 gr of potassium carbonate anhydride are dissolved in 70 ml of DMF and agitated under heating at 50° to 60° C for 16 hours, followed by a normal refining treatment, and the obtained basic material is extracted with chloroform, followed by back extraction with 1% acetic acid solution, and the object material is obtained from the acetic acid layer. It is further recrystallized from hydrous dioxane as a hydrochloride. Melting point (decomposed): 230° C; yield: 0.95 gr. (C 34 H 54 N 4 O 6 .4HCl)
EXAMPLE 9 (n = 8)
9.0 gr of a hydrochloride of the material (II), 3.0 gr of dichlorooctane and 16 gr of potassium carbonate anhydride are dissolved in 70 ml of DMF and agitated under heating at 65° to 70° C for 12 hours, and the mixture is subjected to the same treatment as Example 8 and recrystallized from hydrous isopropanol as a hydrochloride. Melting point (decomposed): above 230° C; yield: 2.2 gr. (C 36 H 58 N 4 O 6 .4HCl)
EXAMPLE 10-a (Z: -CH 2 CH 2 OH)
34 gr of a hydrochloride (melting point: 215° - 222° C) of the material (II) is dissolved under heating in 500 ml of ethanol having dissolved therein 5.0 gr of metallic sodium, and after cooling the mixture and filtering off the insolubles, ethanol is perfectly distilled off under vacuum. The residue is dissolved in 150 ml of DMF and added with 15 gr of β-bromohydrin and further with 15 gr of potassium carbonate anhydride, and the mixture is agitated under heating at 80 to 90° C for 3 hours. After cooling, it is diluted with water and extracted with ethyl acetate and the extract is recrystallized from ethanol as a hydrochloride. Melting point: 220° - 225° C; yield:27.8 gr. (C 16 H 26 N 2 O 4 .2HCl)
EXAMPLE 10-b (Z: -CH 2 CH 2 OH)
10 gr of a hydrochloride of the material (II) is added in 50 ml of ethanol containing 7.5 gr of triethylamine, and the mixture is refluxed under agitation for 30 minutes. After cooling the mixture, 34 ml of ethanol containing 2.0 gr of ethylene oxide is added dropwise under ice cooling and agitation for 10 minutes, followed by additional 3-hour agitation at room temperature. Ethanol is distilled off under vacuum, and the residue is treated in the same way as Example 10-a to obtain 8.8 gr of the object hydrochloride material.
EXAMPLE 10-c (Z: --CH 2 CH 2 OH)
45 gr of 2,3,4-trimethoxybenzaldehyde and 30 gr of N-β-hydroxyethylpiperazine are dissolved in 200 ml of ethanol and agitated under heating for 30 minutes, and the mixture, after cooling, is added with 5.0 gr of hydrogenated sodium borate under agitation and refluxed. This is followed by the same treatment as practiced in Example 10-a to obtain 41 gr of the object material (a hydrochloride).
EXAMPLE 10-d (Z: --CH 2 CH 2 OH)
19.6 gr of 2,3,4-trimethoxybenzaldehyde and 19.5 gr of N-β-hydroxyethylpiperazine are dissolved in 100 ml of ethanol, to which is further added 10 ml of formic acid under reflux, followed by additional 6-hour reflux. The reaction mixture is then subjected to the same treatment as in the preceding examples to obtain 17.0 gr of the object hydrochloride material.
EXAMPLE 10-e (Z: --CH 2 CH 2 OH)
4.33 gr of 2,3,4-trimethoxybenzyl chloride and 3.0 gr of N-β-hydroxyethylpiperazine are dissolved in 50 ml of ethanol, followed by addition of 2.0 gr of potassium carbonate and 6-hour agitation under reflux. The mixture is then subjected to the normal treatment to obtain 3.3 gr of the object material.
EXAMPLE 10-f (Z: --CH 2 CH 2 OH)
50 gr of N,N-bis-62 -chloroethyl-2,3,4-trimethoxybenzylamine hydrochloride (melting point: 127° - 131° C) and 50 gr of monoethanolamine are dissolved in 150 ml of ethanol and refluxed under heating for 30 minutes, followed by a usual refining treatment to obtain 32 gr of the object hydrochloride material.
EXAMPLE 11 ##STR8##
1.33 gr of metallic sodium is dissolved in 100 ml of ethanol, which is further added with 10 gr of a hydrochloride of the material (II) and agitated for 30 minutes. Thereafter, 2.5 gr of propylene oxide is added dropwise for the period of 5 minutes, followed by 1-hour reflux under heating. The mixture is then treated by a usual method to obtain an oily reaction product and this product is treated with hydrochloric acid in ethanol and recrystallized from isopropanol as a hydrochloride. Melting point: 212° - 215° C; yield: 6.5 gr. (C 17 H 28 N 2 O 4 .2HCl1/2H 2 O)
EXAMPLE 12 ##STR9##
1.36 gr of metallic sodium is dissolved in 100 ml of ethanol, and this solution is further added with 10 gr of a hydrochloride of the material (II) and agitated for 30 minutes. Thereafter, 3.26 gr of glycidol is added dropwise for the period of 5 minutes, followed by 2-hour reflux under heating. The mixture is then treateed according to a usual method and the obtained basic material is extracted with n-butanol and the extract is treated with ethanol hydrochloric acid and recrystallized from ethanol as a hydrochloride. Melting point: 215° - 218° C; yield: 6.8 gr. (C 17 H 28 N 2 O 5 .2HCl)
EXAMPLE 13-a ##STR10##
10 gr of a hydrochloride of the material (II) and 7.43 gr of triethylamine are refluxed in 50ml of ethanol under heating for 30 minutes, and after cooling, the mixture is further added with 5.25 gr of styrene oxide dropwise for the duration of 5 minutes and then refluxed under heating for 2 minutes. This is followed by an ordinary treatment and the obtained product is refined by a silica gel column chromatograph and recrystallized from isopropanol as a hydrochloride. Melting point: 170° 14 173° C; (C 22 H 29 N 2 O 5 .2HCl) yield: 3.5 gr. There is also obtained, as a side reaction product, a material of the general formula (I) where R is a methyl group and Z is -C 6 H 5 CHCH 2 OH Melting point of this material (hydrochloride) is 177° - 182° C and yield is 0.7 gr.
EXAMPLE 13-b ##STR11##
0.14 gr of metallic sodium is dissolved in 10 ml of ethanol, which is further added with 2.0 gr of a hydrochloride of the material (II) and agitated for 30 minutes, followed by further addition of 12 gr of potassium carbonate and 1.7 gr of phenacyl bromide and 1-hour reflux under agitation. This mixture is then treated by a usual method to obtain 2.3 gr of an oily reaction product. Thus obtained 2.3 gr of N-phenacyl compound is dissolved in 20 ml of methanol, further added with 300 mg of hydrogenated sodium borate and refluxed. The refluxed material is then agitated at room temperature for 1 hour, further treated by a normal method and recrystallized from isopropanol as a hydrochloride. Melting point: 171° - 173° C; yield: 1.5 gr. (C 22 H 29 N 2 O 5 .2HCl)
EXAMPLE 14 ##STR12##
6.0 gr of a hydrochloride of the material (II) is dissolved in 100 ml of ethanol, then added with 5.0 gr of triethylamine and agitated for 30 minutes. The mixture is further added with 3.75 gr of phenylglycidylether, refluxed under heating for 15 minutes, treated by a usual method and recrystallized from isopropanol as a hydrochloride. Melting point: 180° - 185° C; yield: 5.1 gr. (C 23 H 32 N 2 O 5 .2HCl.1/2H 2 O)
EXAMPLE 15 ##STR13##
1.0 gr of the material (II) and 0.85 gr of α-naphthyl glycidyl are dissolved in 30 ml of dioxane and refluxed for 30 minutes. The reaction solution is distilled under vacuum and the residue is dissolved in isopropanol and HCl gas is passed there-through. The precipitated crystals are filtered off and recrystallized from isopropanol. Melting point (decomposed): 223° - 226° C; yield: 0.95 gr. (C 27 H 36 N 2 O 5 .2HCl)
EXAMPLE 16 ##STR14##
1.0 gr of the material (II) and 0.85 gr of β-naphthyl glycidyl ether are treated in the completely same way as Example 16 to obtain 0.97 gr of the object material. Melting point (decomposed) : 214° - 217° C. (C 27 H 36 N 2 O 5 .2HCl)
EXAMPLE 17 (R: ethyl group (same in Examples 18 through 23) ##STR15##
1.33 gr of metallic sodium is dissolved in 100 ml of ethanol, which is further added with 10 gr of a hydrochloride of the material (III) and agitated for 30 minutes. Thereafter, 2.5 gr of propylene oxide is added dropwise for the period of 5 minutes, followed by 1-hour reflux under heating. The mixture is then treated according to a usual method and the obtained oily material is treated with hydrochloric acid in ethanol and recrystallized from isopropanol as a hydrochloride. Melting point (decomposed): 214° - 218° C ; yield: 7.6 gr.(C 20 H 34 N 2 O 4 .2HCl
EXAMPLE 18 ##STR16##
1.33 gr of metallic sodium is dissolved in 100 ml of ethanol, followed by addition of 10 gr of a hydrochloride of the material (III) and 30-minute agitation for 30 minutes. Thereafter, 3.0 gr of butylene oxide is added dropwise for the period of 5 minutes and the mixture is refluxed under heating from 1 hour. This is followed by a proper treatment according to a usual method and the obtained reaction product is treated with hydrochloric acid in ethanol and recrystallized from isopropanol as a hydrochloride. Melting point : (decomposed): 212° - 215° C; yield: 6.9 gr. (C 21 H 36 N 2 O 4 .2HCl)
EXAMPLE 19 ##STR17##
1.0 gr of the material (III) is dissolved in 30 ml of dioxane, followed by addition of 0.85 gr of α-naphthylglycidylether and 30-minute reflux under heating. The mixture is further treated according to a normal process and recrystallized from isopropanol as a hydrochloride. Melting point (decomposed): 212° - 217° C; (C 30 H 40 N 2 O 5 .2HCl) yield: 1.0 gr.
EXAMPLE 20 ##STR18##
1.0 gr of the material (III) and 0.85 gr of naphthylglycidylether are treated in the completely same was as Example 19 to obtain 1.0 gr of the object material. Melting point (decomposed): 205° - 210° C. (C 30 H 40 N 2 O 5 .2HCl)
EXAMPLE 21 ##STR19##
1.0 gr of the material (III) is dissolved in 30 ml of methanol, and this is further added with 0.75 gr of phenylglycidylether, refluxed under heating for 45 minutes, treated according to a normal method and recrystallized from isopropanol as a hydrochloride. Melting point (decomposed): 209° - 213° C; yield: 1.48 gr. (C 26 H 38 N 2 O 5 .2HCl)
EXAMPLE 22 ##STR20##
A mixture of 2.2 gr of N-3-(4-methoxy)-2-hydroxypropylpiperazine dihydrochloride (m.p. 190°-194° C) and 2.0 gr of 2,3,4-triethoxybenzaldehyde is dissolved in 100 ml of formic acid and the mixture is refluxed at 70-80° C for 24 hours. The reaction solution is evaporated in vacuo, the residue is diluted with water, washed with benzene, made alkaline with sodium hydroxide, and extracted with benzene. The extract is purified by a silica gel column chromatography, converted to a hydrochloride, and recrystallized from ethanol. C 27 H 40 N 2 O 6 .2HCl. Melting point: 199°-204° C (decompn). Yield: 0.61 gr.
EXAMPLE 23 ##STR21##
A mixture of 1.72 gr of 2,3,4-triethoxybenzyl chloride and 1.60 gr of N-3-(2-methylphenoxy)-2-hydroxypropylpiperazine dihydrochloride (m.p. 157°-161° C) is added to 50 ml of DMF and the mixture is heated with 5.0gr of anhydrous potassium carbonate at 60°-70° C for 4 hr with agitation. The reaction mixture is then diluted with dil. hydrochloric acid, washed with benzene, made alkaline with sodium hydroxide, and extracted with benzene. The extract is converted to a hydrochloride and recrystallized from isopropanol. C 27 H 40 N 2 O 5 .2HCl. Melting point: 209°-212° C (decompn). Yield: 1.67 gr.
EXAMPLES 24 TO 40
More 17 compounds are similarly prepared by the process disclosed in the Example 14. They are listed in the following Table 2.
Table 2__________________________________________________________________________ ##STR22##__________________________________________________________________________ExampleNo. R: A: molecular formula M P__________________________________________________________________________24 CH.sub.3 ##STR23## C.sub.23 H.sub.31 N.sub.2 O.sub.5 F . 200-203° C(decomp.)25 " ##STR24## C.sub.23 H.sub.31 N.sub.2 O.sub.5 F . 208-209° C(decomp.)26 " ##STR25## C.sub.23 H.sub.31 N.sub.2 O.sub.5 Cl . 205-206° C(decomp.)27 " ##STR26## C.sub.23 H.sub.31 N.sub.2 O.sub.5 Cl . 207-208° C(decomp.)28 " ##STR27## C.sub.23 H.sub.31 N.sub.2 O.sub.5 Br . 219-221° C(decomp.)29 " ##STR28## C.sub.24 H.sub.34 N.sub.2 O.sub.5 . 206-208° C(decomp.)30 " ##STR29## C.sub.24 H.sub.34 N.sub.2 O.sub.5 . 190-196° C(decomp.)31 " ##STR30## C.sub.25 H.sub.36 N.sub.2 O.sub.5 . 2HCl . H.sub.2 O 205-207° C(decomp.)32 " ##STR31## C.sub.27 H.sub.40 N.sub.2 O.sub.5 . 218-222° C(decomp.)33 " ##STR32## C.sub.24 H.sub.34 N.sub.2 O.sub.6 . 200-202° C(decomp.)34 " ##STR33## C.sub.24 H.sub.34 N.sub.2 O.sub.6 202-205° C(decomp.)35 " ##STR34## C.sub.25 H.sub.36 N.sub.2 O.sub.6 . 2HCl1/2H.sub.2 O 201- 205° C(decomp.)36 " ##STR35## C.sub.30 H.sub.38 N.sub.2 O.sub.6 . 200-202° C(decomp.)37 " ##STR36## C.sub.23 H.sub.32 N.sub.2 O.sub.6 2HCl 220-223° C(decomp.)38 C.sub.2 H.sub.5 ##STR37## C.sub.26 H.sub.37 N.sub.2 O.sub.5 F . 225-229° C(decomp.)39 " ##STR38## C.sub.26 H.sub.37 N.sub.2 O.sub.5 Cl . 210-214° C(decomp.)40 " ##STR39## C.sub.26 H.sub.37 N.sub.2 O.sub.5 Cl . 212-218° C(decomp.)__________________________________________________________________________
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N-substituted trialkoxybenzyl piperazine derivatives expressed by the following general formula (I): ##STR1## where R represents a methyl or ethyl group, and Z represents a group selected from the group consisting of the following groups: isopropenyl group, cinnamyl group, morpholino ethyl group, diaminotriazine group, hydantoinbutyl group, ##STR2## where R represents the same as above, and n is an integer of 2 to 8, and ##STR3## where A represents a group selected from the group consisting of hydrogen, lower alkyl group, hydroxymethyl group, phenyl group, naphthyloxymethyl group and ##STR4## where Y represents a group selected from the group consisting of hydrogen, halogen, lower alkyl group, lower alkoxy group and hydroxy group.
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